A reduced mechanism for primary reactions of coal volatiles in a plug flow reactor

In the present paper, the authors study the primary reactions of coal volatiles and a detailed mechanism has been made for three different environments: thermal decomposition (pyrolysis), partial oxidation (O₂) and O₂/CO₂ gasification in a plug flow reactor to analyze the combustion component. The computed results have similar trend for three different environments with the experimental data. A systematically reduced mechanism for O₂/CO₂ gasification has also been derived by examination of Rate of Production (ROP) analysis from the detailed mechanism (255 species and 1095 reactions). The reduced mechanism shows similar result and has been validated by comparing the calculated concentrations of H₂, CH₄, H₂O, CO, CO₂ and polycyclic aromatic hydrocarbon (PAH) with those of the detailed mechanism in a wide range of operating conditions. The authors also predicted the concentration profiles of H₂, CO, CO₂ and PAH at high temperature and high pressure.     

Subcooled Flow Boiling Heat Transfer to Water and Ethylene Glycol/Water Mixtures in a Bottom-heated Tube

Subcooled flow boiling heat transfer experiments were performed with water and ethylene glycol/water mixtures at five flow velocities and four fluid inlet temperatures. Both turbulent flow and laminar flow were tested in a special test facility with its experimental test section heated from the bottom surface only. Boiling curves and subcooled flow boiling heat transfer coefficients of the tested fluids were determined from the experimental measurements. Predictive correlations of the subcooled flow boiling heat transfer coefficients were developed based on the experimental data. Comparisons are presented of wall temperatures between the experimental measurements and the correlation predictions.     

Analysis of first stage ignition delay times of dimethyl ether in a laminar flow reactor

The combustion chemistry of the first stage ignition and chemistry/flow interactions are studied for dimethyl ether (DME) with a mathematical analysis of two systems: a plug flow reactor study is used to reduce the reaction chemistry systematically. A skeletal reaction mechanism for the low temperature chemistry of DME until the onset of ignition is derived on the basis of the detailed DME mechanism of the Lawrence Livermore National Laboratory – see Curran, Fischer and Dryer, Int. J. Chem. Kinetics, Vol. 32 (2000). It is shown that reasonably good results for ignition delay times can be reached using a simple system of three ordinary differential equations and that the resulting analytical solution depends only on two reaction rates and the initial fuel concentration. The stepwise reduction of the system based on assumptions yields an understanding on why these reactions are so important. Furthermore, the validation of the assumptions yields insight into the influence of the fuel and the oxygen concentration on the temperature during the induction phase. To investigate the influence of chemistry/flow interactions, a 2D model with a laminar Hagen–Poiseuille flow and 2D-polynomial profiles for the radial species concentration is considered. For the 2D model, it is found that only the diffusion coefficients and the reactor radius need to be taken into consideration additionally to describe the system sufficiently. Also, the coupling of flow and chemistry is clarified in the mathematical analysis. The insight obtained from the comparison of the 2D model and the plug flow model is used to establish an average velocity for the conversion of ignition locations to ignition delay times in a laminar flow reactor. Finally, the 2D analytical solution is compared against new experimental data, obtained in such a laminar flow reactor for an undiluted DME/air mixture with an equivalence ratio of φ = 0.835 and a temperature range of 555 to 585 K at atmospheric pressure.     

The effect of CO on CO2-char gasification

The effect of CO on the gasification of a Polish coal-derived char was investigated in a fluidised bed from 1123 to 1248 K. Rate expressions developed from Ergun's mechanism or a modified three-step reaction mechanism, coupled with Cylindrical Pore Interpolation Model (CPIM) to account for the intra-particle mass transfer, were developed to predict gasification and the effect of CO. Compared to the Ergun's rate expression, the three-step expression has an extra term for p_co, making the inhibition effect of CO more pronounced. The agreement between experimental and numerical results was satisfactory for both models simulating gasification by CO₂/N₂. Then, when CO (1% or 3%) was intentionally introduced in the feed gas (CO₂/N₂), the gasification rates significantly decreased. It was found that the model based on Ergun's mechanism over-estimated the gasification rate, while the results from the model with the three-step mechanism agreed with the experimental data.     

Modeling high pressure ethane oxidation and pyrolysis

A previously developed detailed chemical kinetic model for ethane oxidation and pyrolysis has been extended by considering the impact of much higher pressures on the chemically- and thermally-activated reactions in the mechanism. The resulting mechanism is now compared to data at much higher pressures. These data include both ethane oxidation and pyrolysis shock tube experiments up to pressures of 986 atm as well as autoignition and ethane dissociation data near 10 atm. The temperature and pressure dependencies of the rate coefficients in the model are represented by Chebyshev polynomials. This model, with no adjustments, describes the varied experimental data very well. A first order sensitivity analysis identified the most important reactions in each of the kinetic regimes. These results, coupled with the earlier validation studies at lower pressures, suggest this model is broadly applicable to analysis of ethane pyrolysis and oxidation over very wide temperature and pressure ranges.     

A functional-group-based approach to modeling real-fuel combustion chemistry – III: Application to biodiesels

Real biodiesel fuels are mixtures comprising many high molecular weight components, making it a challenge to predict their combustion chemistry with detailed kinetic models. Our group previously proposed a functional-group approach (FGMech) to model the combustion chemistry of real gasoline and jet fuels; this approach has now been extended to model real biodiesel combustion and mixtures with petroleum fuels. As in our previous work, a decoupling philosophy is adopted for construction of the model. A lumped reaction mechanism describes the (oxidative) pyrolysis of fuels, while a detailed base chemistry model represents the oxidation of key pyrolysis intermediates. However, due to the presence of the ester group, several oxygenated species are identified as additional primary products and incorporated into the lumped reaction steps. In addition to the lumped reactions initiated by unimolecular decomposition and H-atom abstraction reactions, a lumped H-atom addition-elimination reaction is also incorporated as a new reaction class to account for the presence of double bonds. Stoichiometric parameters are obtained based on a multiple linear regression (MLR) model, which establishes relationships between the fuel's functional group distributions and the stoichiometric parameters of the lumped reactions. Global rate constants are developed from consistent rate rules obtained from pure fuels. New pyrolysis experimental data for methyl pentanoate/methyl nonanoate and methyl heptanoate/n-heptane mixtures (50%/50% in mol) are obtained in a jet-stirred reactor at atmospheric pressure. In general, kinetic models developed using the FGMech approach can reasonably reproduce all the validation targets obtained in this work, as well as those in the literature, confirming that functional-group-modeling is a promising approach to simulate combustion behavior of diesel/biodiesel surrogate fuels and real biodiesels.     

Quantifying the effect of CO2 gasification on pulverized coal char oxy-fuel combustion

Previous research has provided strong evidence that CO₂ and H₂O gasification reactions can provide non-negligible contributions to the consumption rates of pulverized coal (pc) char during combustion, particularly in oxy-fuel environments. Fully quantifying the contribution of these gasification reactions has proven to be difficult, due to the dearth of knowledge of gasification rates at the elevated particle temperatures associated with typical pc char combustion processes, as well as the complex interaction of oxidation and gasification reactions. Gasification reactions tend to become more important at higher char particle temperatures (because of their high activation energy) and they tend to reduce pc oxidation due to their endothermicity (i.e. cooling effect). The work reported here attempts to quantify the influence of the gasification reaction of CO₂ in a rigorous manner by combining experimental measurements of the particle temperatures and consumption rates of size-classified pc char particles in tailored oxy-fuel environments with simulations from a detailed reacting porous particle model. The results demonstrate that a specific gasification reaction rate relative to the oxidation rate (within an accuracy of approximately +/- 20% of the pre-exponential value), is consistent with the experimentally measured char particle temperatures and burnout rates in oxy-fuel combustion environments. Conversely, the results also show, in agreement with past calculations, that it is extremely difficult to construct a set of kinetics that does not substantially overpredict particle temperature increase in strongly oxygen-enriched N₂ environments. This latter result is believed to result from deficiencies in standard oxidation mechanisms that fail to account for falloff in char oxidation rates at high temperatures.     

适用于HCCI燃烧的PRF化学动力学骨架机理

本文构建了一个适用于HCCI燃烧的PRF化学反应动力学骨架机理。该机理包含40种组分和65个反应。通过与激波管、喷射搅拌反应器、流动反应器和HCCI发动机的实验数据对比表明,新机理适用于多种反应器,可以较准确地计算着火点及关键组分的演变规律,并且在不同的温度、压力和当量比下具有较好的性能。在HCCI发动机的单区模型计算中,对于燃料PRF 91.8和PRF 70,骨架机理计算结果与Curran等人的详细机理计算结果基本相同。     

Evaluation of reduced combustion kinetic mechanisms using global sensitivity-based similarity analysis (GSSA)

Reduced combustion kinetic mechanisms, instead of detailed ones, are often used in computational fluid dynamics (CFD) simulations for reduced and frequently even affordable computational cost. The criterion for the evaluation of a reduced mechanism usually focuses on its prediction error for the global properties such as the ignition delay time, while ignoring the detailed features of reaction kinetics such as reaction pathways. In our opinion, good reduced mechanisms should have similar predicting behaviors as the detailed ones, and these behaviors include model predictions for specific targets, prediction error bars, and uncertainty sources for the errors. In this work, a new approach using global sensitivity-based similarity analysis (GSSA) is proposed to compare reduced mechanisms with detailed ones. The similarity coefficient for the reduced mechanism is calculated by similarity method based on Euclidean distance between sensitivity indices of the reduced mechanism and those of the detailed mechanism. The larger the similarity coefficient, the higher the degree of similarity between the reduced and detailed mechanisms. To demonstrate this similarity method, directed relation graph with error propagation (DRGEP) is employed to simplify both the GRI 3.0 mechanism without the NOx chemistry and the JetSurF mechanism consisting of 1459 reactions, resulting in reduced mechanisms with different sizes which can accurately predict the ignition delay times for corresponding fuel mixtures. Similarity analysis is then employed to evaluate these reduced mechanisms. The result shows that the actual reaction kinetic features cannot be replicated by some of the reduced mechanisms. First, the rankings of the important reactions obtained by reduced mechanisms are not consistent with those obtained by the detailed mechanism. Second, by investigating the sensitive reactions, the actual impact of uncertainties in reaction rates on the ignition delay times cannot be presented by reduced mechanisms. The similarity analysis on reduced mechanisms can be used to select a reduced mechanism which shows much better performance to replicate the actual combustion reaction kinetics. GSSA can provide information on the uncertainty sources induced by the reactions parameters of reduced mechanisms for target predictions, which is important for further reduced model optimization and for the sensitivity analysis of CFD simulations.     

Enzymatic synthesis of multi-component copolymers and their structural characterization

The use of enzymes in synthetic applications has increased dramatically in the recent years and the field of polymer science is part of this trend. Synthesis of a variety of polymers using lipase catalyzed (Candida antarctica) polymerization reactions has led to a variety of new materials with interesting properties in our laboratories. This paper describes the synthesis of multi-component polyesters and mixed polymers having polyester and polyamide linkages under solvent-less conditions using Candida antarctica lipase B. The effect of a third component, i.e. a series of 1,omega-alkanediols (1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol and 1,16-hexadecanediol) on the copolymerization reaction of dimethyl 5-hydroxyisophthalate with poly(ethylene glycol 600) has been studied and the mechanism for the incorporation of the third component is proposed. We have also studied the effect of different functional groups during terpolymerization reaction of dimethyl 5-hydroxyisophthalate with poly(ethylene glycol) by adding a third component having different functionalities (1,6-hexanediol, 1,6-hexanediamine or 1,6-hexanedithiol) and compared the effect of hydroxyl, amine and thiol groups on the polymerization reactions.     

光解杜醌/氢给体均相体系的CIDEP研究

以杜醌为光敏剂,用高时间分辨电子自旋共振 (TRESR)波谱仪研究了杜醌/乙二醇体系、杜醌/氮氧自由基/乙二醇体系的化学诱导动态电子自旋极化(CIDEP).实验表明,紫外激光照射下,在杜醌/乙二醇溶液中得到以三重态机理极化为主的中性杜半醌自由基DQH*和以碳为中心的乙二醇碳自由基R*(OH)2的极化信号,而加入氮氧自由基 TEMPO后,则只观测到极化的TEMPO的E+E/A极化谱,其产生机理属于以四重态为先驱的自由基-三重态对极化机理(QP-RTPM),结合极化强度的理论计算对该体系的极化形成过程进行了分析.     

Understanding soot particle size evolution in laminar ethylene/air diffusion flames using novel soot coalescence models

Two coalescence models based on different merging mechanisms are introduced. The effects of the soot coalescence process on soot particle diameter predictions are studied using a detailed sectional aerosol dynamic model. The models are applied to a laminar ethylene/air diffusion flame, and comparisons are made with experimental data to validate the models. The implementation of coalescence models significantly improves the agreement of prediction of particle diameters with the experimental data. Sensitivity of the soot prediction to the coalescence parameters is analysed. Finally, an update to the coalescence model based on experimental observations of soot particles in the flame oxidation regions has been introduced to improve its predicting capabilities.     

Viscosity and Temperature Effects on the Rate of Oxygen Quenching of Tris-(2,2′-bipyridine)ruthenium(II)

We compare the bimolecular quenching rate constant (k₂) of luminescent tris(2,2′-bipyridine)ruthenium(II) by oxygen in water, ethylene glycol and glycerol as a function of temperature and viscosity to several theoretical models. The Smoluchowski equation with experimentally determined diffusion coefficients produced calculated values that were in the best agreement with experiment. For the less viscous solvent, water, this equation produced a value that was approximately an order of magnitude larger than the experimental value. With an increase in solvent viscosity, the Smoluchowski value approached the experimental value. Using the Smoluchowski equation with calculated diffusion coefficients based on the known radii of the reacting species produced deviations an order of magnitude larger in water and a factor of two or three lower in ethylene glycol and glycerol. If an assumption is made that the radii of both molecules are equal, we have the Stokes Einstein equation, and the only parameters become temperature and viscosity. Using this relationship, the calculated values for water are about a factor of two larger and with ethylene glycol and glycerol about a factor of 6 smaller than experimental data. These results show that bimolecular quenching is a more complex process affected by many parameters such as solvent cage effects in addition to viscosity and temperature.     

Molecular mechanism of gelation with ethylene glycol added to a solution of polyacrylonitrile in dimethylsulfoxide

The mechanism of solidifying a solution of polyacrylonitrile (PAN) in dimethylsulfoxide (DMSO) into which ethylene glycol is added is studied by the method of Raman spectroscopy. In the absence of ethylene glycol, DMSO molecules produce dipole-dipole bonds to PAN molecules. Upon adding ethylene glycol, DMSO molecules form hydrogen bonds with it and a line at 1000 cm⁻¹ appears in the Raman spectrum, which is assigned to the valence vibrations of S=O bonds involved in the hydrogen bonds. After DMSO is removed, ethylene glycol molecules produce hydrogen bonds with two neighboring PAN molecules, giving rise to a band at 2264 cm⁻¹, which is assigned to the valence vibrations of C≡N bonds involved in these hydrogen bonds. A high-viscosity gel consisting of PAN molecules arises in which these molecules are bonded to each other through ethylene glycol molecules.     

几种氧化物纳米流体强化传热性能研究

以水/乙二醇混合液为基液,加入A12O3,MgO和ZnO纳米颗粒配制得到纳米流体.在自制对流传热性能测试平台上进行基液及纳米流体传热性能的测试.结果表明:同基液相比,随流体流速增大,A12O3纳米流体的传热系数变化不明显,MgO和ZnO纳米流体的传热系数均有提高.层流状态下,随雷诺数增大,三种纳米流体的传热系数都不断增...     

Effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions

The effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions was studied by single particle experiments and modelling. Experiments of pine and beech wood char conversion were carried out in a single particle combustor under conditions of 1473-1723 K, 0.0-10.5% O₂, and 25-42% H₂O. A comprehensive progressive char conversion model, including heterogeneous reactions (char oxidation and char gasification with CO₂ and H₂O), homogeneous reactions (CO oxidation, water-gas shift reaction, and H₂ oxidation) in the particle boundary layer, particle shrinkage, and external and internal heat and mass transfer, was developed. The modelling results are in good agreement with both experimental char conversion time and particle size evolution in the presence of oxygen, while larger deviations are found for the gasification experiments. The modelling results show that the char oxidation is limited by mass transfer, while the char gasification is controlled by both mass transfer and gasification kinetics at the investigated conditions. A sensitivity analysis shows that the CO oxidation in the boundary layer and the gasification kinetics influence significantly the char conversion time, while the water-gas shift reaction and H₂ oxidation have only a small effect. Analysis of the sensitive parameters on the char conversion process under a typical pulverized biomass combustion condition (4% O₂, 13% CO₂, 13% H₂O), shows that the char gasification reactions contribute significantly to char conversion, especially for millimeter-sized biomass char particles at high temperatures.     

Dynamics of flow–soot interaction in wrinkled non-premixed ethylene–air flames

A two-dimensional simulation of a non-premixed ethylene–air flame was conducted by employing a detailed gas-phase reaction mechanism considering polycyclic aromatic hydrocarbons, an aerosol-dynamics-based soot model using a method of moments with interpolative closure, and a grey gas and soot radiation model using the discrete transfer method. Interaction of the sooting flame with a prescribed decaying random velocity field was investigated, with a primary interest in the effects of velocity fluctuations on the flame structure and the associated soot formation process for a fuel-strip configuration and a composition with mature soot growth. The temporally evolving simulation revealed a multi-layered soot formation process within the flame, at a level of detail not properly described by previous studies based on simplified soot models utilizing acetylene or naphthalene precursors for initial soot inception. The overall effect of the flame topology on the soot formation was found to be consistent with previous experimental studies, while a unique behaviour of localised strong oxidation was also noted. The imposed velocity fluctuations led to an increase of the scalar dissipation rate in the sooting zone, causing a net suppression in the soot production rate. Considering the complex structure of the soot formation layer, the effects of the imposed fluctuations vary depending on the individual soot reactions. For the conditions under study, the soot oxidation reaction was identified as the most sensitive to the fluctuations and was mainly responsible for the local suppression of the net soot production.     

Erratum

Modelling of pulverised wood flames in a laboratory vertical furnace was carried out. The aim was to gain deeper understanding of the combustion process and to validate a mathematical model to simulate the process. Pulverised wood combustion involves many different processes such as two-phase flow dynamics, drying and devolatilisation of the particles, oxidation of the volatile and formation and oxidation of char. It is desirable to know which are the most dominating/sensitive processes that control the combustion behaviour and in particular the emissions of unburned hydrocarbons and carbon monoxide. To achieve this goal, a comprehensive devolatilisation model based on the functional group concept is applied to predict the details of the devolatilisation products including tar. The solid-gas coupling is made using the Eulerian/Lagrangian approach. A ‘rocket force’ model is developed to account for the influence of drying and devolatilisation on the particle motion. The present mathematical model successfully simulated the flame temperature and detailed species distributions including CH₄ and CO. These two species were shown to be sensitive to the fate of tar. Major paths for the CO formation were identified as the devolatilisation of the wood particles and the char oxidation. Influences of the initial functional group yield, the char oxidation and gasification reactions, the turbulence mixing rate and the fuel particle size on the flame structures andb emissions were examined.     

用于乙烯环氧化反应的CuCs掺杂银基催化剂设计

最近的理论研究筛选出CuCs掺杂Ag基催化剂是一种高效的乙烯环氧化催化剂[ACS Catal. 11,3371 (2021)]. 然而,该工作是基于研究表面建模预测Ag基催化剂的性能,在实际反应过程中,Ag基催化剂是颗粒状的. 本文结合密度函数理论、Wulff构造理论和微观动力学分析来研究Ag基催化剂在颗粒模型上的催化性能. 研究表明,CuCs掺杂Ag基催化剂在选择性和活性方面都优于纯Ag基催化剂,这一点通过实验得到了证明. 进一步地表征分析发现,CuCs掺杂能促进颗粒的生长以及颗粒的分散,从而形成富含晶界的Ag颗粒. 此外,CuCs促进了催化剂表面亲电氧的形成,这均有利于环氧乙烷的形成和解吸. 本工作为理论与实验相结合的催化剂设计提供了一个案例研究.     

正丁烷燃料中低温氧化的骨架反应机理

本文基于Healy等人建立的正丁烷详细反应机理(230个组分,1328个反应),采用直接关系图法,反应路径分析以及敏感性分析相结合的方法,构建了一个包含83个组分,397个反应的中低温反应动力学骨架模型。路径分析发现,在低温反应中,正丁烷氧化着火主要受链传播反应中的放热循环控制。而在中温反应中,正丁烷及其下游产物正丁基的裂解反应变得重要,大分子裂解后的小分子氧化加快反应进程。本文骨架模型在温度范围550~1050 K、压力范围0.1~3MPa、当量比范围0.5~2.0条件下对着火延迟时间、层流火焰速度、温度以及重要组分浓度分布的预测均与详细机理保持很好的一致性,同时与文献中快压机、定容燃烧弹和搅拌射流反应器的实验结果也吻合较好。