基于红外光谱研究沥青燃烧机理和有害气体成分分析

利用Rosemount气体分析仪和定碳炉搭建起固定床燃烧反应试验平台,通过红外光谱分析技术定量分析沥青及其胶浆在高升温速率条件下燃烧反应的有毒气态产物成分、及其释放规律。研究表明,在高升温速率、近等温条件下,沥青及胶浆的燃烧过程可近似分为活泼挥发组分析出燃烧、二次挥发析出结合残炭燃烧两个阶段,其主要气态产物为CO₂,CO,NO,NO₂及SO₂。沥青材料中活泼挥发组分含量是影响燃烧气态产物释放规律的关键因素之一,减少沥青材料中活泼挥发组分的含量可有效降低燃烧气态产物的生成、尤其是CO的产生。     

Non-isothermal kinetics of styrene-butadiene-styrene asphalt combustion

The combustion characteristics of styrene-butadiene-styrene （SBS） asphalt are studied by thermogravimetric analysis （TG/DTG） at four different heating rates. According to the saturates/aromatics/resins/asphaltenes （SARA） fractionation method, the combustion process of SBS asphalt can be divided by Gaussian peak fitting into three main stages： oil content release, resin pyrolysis, and asphaltene and char combustion. When the heating rate increases, the mass losses of the oil content and resin pyrolysis increase, and less asphaltenes are formed at a higher temperature. The activation energy values are calculated by the Coats-Redfern method to be in the range 61.6 kJ/mol-142.9 kJ/mol. The Popescu method is used for the kinetic analysis, and the result shows that the three stages of asphalt combustion can be explained by the sphere phase boundary reaction model, the second order chemical reaction model, nucleation, and its subsequent growth model, respectively.     

Measurement and kinetics of elemental and atomic potassium release from a burning biomass pellet

Combining polarizing-filtered planar laser-induced fluorescence (PLIF) with simultaneous laser absorption, quantitative laser-induced breakdown spectroscopy (LIBS) and two-color pyrometry, the potassium release during the combustion of biomass fuels (corn straw and poplar) has been investigated. The temporal release profiles of volatile atomic potassium and potassium compounds from a corn straw show a single peak. The woody biomass, poplar, produces a dual-maxima distribution for potassium and potassium compounds. For both biomass samples, the highest concentrations of released atomic potassium and potassium compounds occur in the devolatilization stage. The mass ratios between volatile atomic potassium and potassium compounds in the corn straw and poplar cases are 0.77% and 0.79%, respectively. These values agree well with chemical equilibrium predictions that 0.68% of total potassium will be in atomic form. A two-step kinetic model of potassium release has been developed, which gives better predictions during the devolatilization stage than the existing single-step model. Finally, a map of potassium transformation processes during combustion is developed. Starting with inorganic and organic potassium, there are eight proposed transformation pathways including five proposed release pathways that occur during the combustion. The pathways describe the transformation of potassium between the fuel volatile matter, char, and ash. Potassium release during the devolatilization stage is due to pyrolysis and evaporation; during the char burnout stage, potassium release is due to char oxidation and decomposition; and during the ash cooking stage, potassium release is caused by reactions between the ash and H₂O in the co-flow.     

Experimental and numerical investigations on the interactions of volatile flame and char combustion of a coal particle

The model that takes chemical reactions, heat and mass transfers in the boundary layer of the particle into account simultaneously, is developed for simulating the combustion of a pulverized coal particle. The FTIR in situ temperature-measurements and the comparison between numerical simulations for the pulverized coal and the devolatilized char show that the volatile flame induces the combustion of the primary product of surface oxidation CO. Due to the influence of volatile flame, the char particle can be ignited at temperature lower than its heterogeneous ignition temperature, which elucidates the physical essence of joint hetero-homogeneous ignition mode discovered by Jüntgen.     

Flame characterisation of gas-assisted pulverised coal combustion using FPV-LES

A multiphase flamelet/progress variable (FPV) model for the large eddy simulation (LES) of gas-assisted pulverised coal combustion (PCC) is developed. The target of the simulation is the Darmstadt turbulent gas-assisted swirling solid fuel combustion chamber. The coal particles are treated as Lagrangian point particles, the position, momentum and energy of which are tracked. The gas phase is described by the low-Mach Navier-Stokes equations alongside the Eulerian transport equations of the governing variables for the FPV model. The set of chemical states of the PCC flame is pre-tabulated in a six-dimensional flamelet table and determined by the mixing of the primary fuel stream, volatiles and char off-gases with the oxidising air, the progress of chemical reactions, the interphase heat transfer, as well as sub-grid scale variations. A presumed $\beta$-PDF approach for the total mixture fraction is applied to capture sub-grid scale effects. The discrete ordinate method (DOM) with the weighted sum of grey gases model (WSGGM) is employed to model radiation. The FPV-LES results are validated against the experimental evidence and a good agreement of the predicted mean and RMS velocities, as well as the mean gas temperature between experiments and simulations is obtained. The contributions of the pilot, volatile and char off-gas fuel streams to the coal flame are analysed. It is found that most regions of the furnace are dominated by either pilot or volatile combustion, while char conversion only occurs in the far downstream and outer furnace regions. The pilot gas dominates the near-wall region inside the quarl, whereas the volatile gas mainly released from small particles dominates a first volatile combustion zone in the interior of the internal recirculation zone. Larger particles heat up more slowly and release their volatile content further downstream, leading to a secondary volatile combustion zone.     

木质装饰板材贫氧条件下燃烧和热解特性研究

本文利用热重差热分析仪,在各种不同的氧气浓度下对落叶松、红木和红松样品进行实验。通过对TG、DTG和DTA曲线的分析,样品干燥基要经历两个失重过程,第一个失重过程主要是纤维素和半纤维素的热解,第二个失重过程主要是木质素的炭化分解和燃烧。在各氧气浓度条件下,热解失重的第一个阶段TG和DTG曲线差异很小;在各样品失重的第二个阶段,随着氧气浓度的增加,TG和DTG曲线左移,反应结束的温度明显降低。氧气能使木质素的炭化物氧化并进而可能使其着火燃烧,从而使反应进程加快。当氧气浓度大于6.32%时,各样品DTA曲线上均有两个明显放热峰,并且随着氧气浓度的增加,DTA曲线放热峰越尖锐,放热峰面积越大,说明氧气浓度越大,在两阶段失重过程中更多的挥发分物质和固体炭化物参与燃烧。     

煤基化学链燃烧过程中硫的演变

在双阶段流化床反应器内,基于溶胶凝胶法制备的Fe2O3/Al2O3氧载体研究了褐煤化学链燃烧过程中燃料硫的迁移路径及分布特性,并讨论了温度、过氧系数对燃料硫释放分布的影响.结果表明:所有工况下,氧载体均未出现被硫化的现象;在热解气化学链燃烧阶段,气相含硫物质以SO2和H2S为主,煤焦气化气化学链燃烧阶段绝大部分为SO2气体,部分来源于煤焦中CaSO4的分解。另外,部分燃料硫被碱金属固定于煤灰中。同时,提高温度和过氧系数都能导致SO2/H2S值和SO2释放量增大。     

Mathematical model of oil shale particle combustion

At first this paper simply introduces the ignition mechanism and combustion characteristics of Huadian oil shale. Combustion behaviour was found to be homogeneous at the beginning of combustion, shifting to heterogeneous combustion in the high-temperature stage; combustible matter was noted to be volatile in the low-temperature stage, but in the high-temperature stage combustible matter included fixed carbon and residual volatile. On the basis of the combustion characteristics of Huadian oil shale, homogeneous and heterogeneous combustion processes of Huadian oil shale are modelled. In the mathematical models, conductive, convective and radiative heat transfer between particles and the surrounding atmosphere, pyrolytic heat and also the heat value of the volatiles are all included in the energy equations; inference of volatile release to particle density is also considered in the models. Thermogravimetric experimental data are used to validate the described models.     

An investigation of the thermal and catalytic behaviour of potassium in biomass combustion

Potassium, a key nutrient in biomass growth, contributes to problematic ash chemistry and corrosion in combustion. This study seeks to examine the behaviour and fate of potassium in biomass combustion under high temperature flame conditions. A model to predict potassium release is presented. Short rotation willow coppice was treated to reduce metals, by water-washing, and remove them, by demineralisation, and then potassium was doped into the demineralised sample. The resultant fuels have been studied for their combustion behaviours in methane–air flames, both as suspended, moving particles, and as stationary, supported particles, using high speed digital video. In the latter case, potassium release was measured simultaneously by emission spectroscopy. In both experiments, potassium was seen to catalyse devolatilisation, and for the stationary particles it was possible to detect potassium catalysis in the char burn-out rates. Demineralised willow was seen to melt in the flame and combustion resembled heavy oil combustion, rather than solid fuel combustion. The residual char was extremely slow to burn-out. In the potassium-doped particles, potassium was seen to evolve over three regimes, devolatilisation, char burn-out and, less significantly, during ash cooking. The first two evolution processes have been modelled using an apparent first order devolatilisation rate for the first stage, and a KOH evaporation model for the second stage.     

Single particle ignition and combustion of pulverized pine wood,wheat straw,rice husk and grape pomace

This work examines the combustion behavior of single pulverized biomass particles from ignition to early stages of char oxidation. The biomass residues investigated were pine wood, wheat straw, rice husk and grape pomace. The biomass particles, in the size range 224–250 µm, were injected upward into a confined region with hot combustion products, produced by a flat flame McKenna burner, with a mean temperature of 1610 K and a mean O₂ concentration of 6.5 vol%. Temporally and spectrally resolved images of the single burning particles were recorded with an intensified charge-coupled device camera equipped with different band-pass spectral filters. Data are reported for CH*, C₂*, Na* and K* chemiluminescence, and thermal radiation from soot and char burning particles. The data on CH* and C₂* chemiluminescence and soot thermal radiation permits to identify important differences between the ignition delay time, volatiles combustion time and soot formation propensity of the four biomass residues, which are mainly affected by their volatile matter content. The Na* and K* emission signals follow the same trends of the CH* and C₂* emission signals until the end of the volatiles combustion stage, beyond which, unlike the CH* and C₂* emission signals, they persist owing to their release from the char burning particles. Moreover, during the volatiles combustion stage, the Na*/CH* and K*/CH* ratios present constant values for each biomass residue. The CH* and thermal radiation emission data suggest that all biomass char particles experienced heterogeneous oxidation at or immediately after the extinction of the homogeneous volatiles combustion.     

Insight into the calcium carboxylate release behavior during Zhundong coal pyrolysis and combustion

In this paper, the dynamic behavior of calcium carboxylate release during Zhundong coal pyrolysis and combustion is studied via reactive molecular dynamics (ReaxFF MD) simulation. The molecular structure model of Zhundong coal is constructed based on the combination of the classic Hatcher coal model and experimental characterizations. Pyrolysis simulations on the coal model are performed at different temperatures ranging from 2000 K to 2800 K. The pyrolysis experiments are also carried out to validate the ReaxFF simulation. The results show that most of the calcium are released into the volatiles by the thermal decomposition of CM-Ca (coal/char matrix with calcium bonded) after releasing CO₂. The distributions of the calcium bonded to gas, tar and inorganics as well as the atomic calcium in the volatiles are quantitatively classified. The thermal cracking of tar fragments are significant at high temperatures leading to the conversion of calcium from tar into the organic gas. Furthermore, the nascent char model is constructed to study the release behavior of calcium in char combustion stage. The calcium is initially released in the form of oxidized calcium and atomic calcium. With increasing temperature, the oxidized calcium trends to convert to the organically bonded calcium. By using the Arrhenius expression, the kinetic parameters for the release of calcium into various species during pyrolysis and char combustion stages are quantitatively determined.     

Particle temperature and potassium release during combustion of single pulverized biomass char particles

This work investigated the combustion characteristics of single pulverized biomass-derived char particles. The char particles, in the size range 224–250 µm, were prepared in a drop tube furnace at pyrolysis temperatures of 1273 or 1473 K from four types of biomass particles – wheat straw, grape pomace, kiwi branches and rice husk. Subsequently, the char particles were injected upward into a confined region of hot combustion products produced by flat flames stabilized on a McKenna burner, with mean temperatures of 1460, 1580 and 1670 K and mean O₂ concentrations of 4.5, 6.5 and 8.5 vol%. The data reported include particle temperature, obtained using a two-color pyrometry technique, and potassium release rate, measured using a laser-induced photofragmentation fluorescence imaging technique. In addition, particle ignition delay time and burning time, obtained from the temporal evolution of the thermal radiation intensity of the burning char particles, are also reported. The results indicated that ignition of the char particles occurs simultaneously with the starting of the potassium release, then the particle burning intensity increases rapidly until it reaches a maximum, after which both the particle temperature and the potassium release rate remain approximately constant until the end of the char oxidation process. The char ignition process is temperature controlled, and the char oxidation process is oxygen diffusion controlled, with the total potassium release being independent of the oxygen concentration and the temperature of the combustion products. The combustion behavior of the chars studied is more affected by the char type than by the conditions used to prepare them.     

基于简单碰撞理论煤粉燃烧动力学模型的研究 -PARTⅠ:理论建模与热重实验

本文根据反应动力学的简单碰撞理论(SCT),建立了气固两相反应通用模型,进一步研究了煤焦燃烧和燃尽的统一动力学模型;粉煤悬浮燃烧时挥发分的析出模型也可包含在该模型中;该模型充分考虑了粉煤在热天平中与在炉内燃烧条件下氧气浓度和氧气可达比表面积变化规律的差异,并给出了计算活化能函数和氧气可达比表面积的新方法,可提高利用热天平获取的动力学参数对炉内煤粉燃烧速率预报的准确性。通过热重分析和已经报道的试验数据对模型的合理性进行了检验。     

Investigating particle and volatile evolution during pulverized coal combustion using high-speed digital in-line holography

Devolatilization is an important process in pulverized coal combustion because it affects the ignition, volatile combustion, and subsequent char burning and ash formation. In this study, high-speed digital in-line holography is employed to visualize and quantify the particle and volatile evolution during pulverized coal combustion. China Shanxi bituminous coal particles sieved in the range of 105–154 µm are entrained into a flat flame burner through a central tube for the study. Time-resolved observations show the volatile ejection, accumulation, and detachment in the early stage of coal combustion. Three-dimensional imaging and automatic particle extraction algorithm allow for the size and velocity statistics of the particle and stringy volatile tail. The results demonstrate the smaller particle generation and coal particle swelling in the devolatilization. It is found that the coal particles and volatiles accelerate due to the thermal buoyancy and the volatiles move faster than the coal particles. On average, smaller particles move faster than the larger ones while some can move much slower possibly because of the fragmentation.     

Insight into KOH and KCl release behavior of burning wood and straw pellets using quantitative in situ optical measurements

Two-dimensional laser-induced photofragmentation fluorescence (LIPF) was employed to quantitatively visualize the potassium hydroxide (KOH) and potassium chloride (KCl) vapor in the plume above burning wood and straw pellets. In the LIPF measurement, two excitation lasers at 266 and 193 nm were adopted to discriminate KOH and KCl. Meanwhile, tunable diode laser absorption spectroscopy (TDLAS), laser-induced breakdown spectroscopy (LIBS) and two-color pyrometry were used to measure the atomic potassium concentration, total elemental potassium concentration and surface temperature of the burning pellets, respectively. The combustion environment had a temperature of 1550 K and an oxygen concentration of 4.6 vol.%. Two peaks were observed from the temporal potassium release profile of the burning wood, corresponding to the devolatilization and char oxidation stage, while only a single release peak was observed from the burning straw attributed to its high ash content. During the char oxidation and ash cooking stages, KOH was observed to be the dominant potassium species released from the wood, while only KCl was observed for the straw which had a high content of chlorine. About 45% of the total potassium in the wood samples and about 10% in the straw samples were measured to be released during the combustion process. The high content of silicon in the straw retained a considerable amount of potassium in the ash. The wood had the potassium release mainly in the char oxidation stage (∼53% of the total release), while the straw had the main release during the ash cooking stage (∼49% of the total release). During the char oxidation and ash cooking stages, about 32% of Cl was released from the straw pellets in KCl, while the other part of Cl was considered to be released during the devolatilization stage in other Cl species form, such as HCl.     

An in-situ method for time-resolved sodium release behaviour during coal combustion and its application in industrial coal-fired boilers

To mitigate the slagging, fouling and high-temperature corrosion problems caused by alkali metals during coal combustion process, measurement of time-resolved alkali metals release is very important. The paper proposed an in-situ approach for measuring sodium (Na) release in coal combustion by Flame Emission Spectroscopy (FES). Through the analysis of spontaneous emission spectra and a calibration procedure, the concentration of gas phase Na, temperature and thermal radiation can be obtained. Firstly, experimental measurement of Zhundong coal particles burning in a flat flame burner was done. Two kinds of Zhundong coal with similar proximate and ultimate analyses, but different ash composition were used. The Na-release history measured by FES was compared with that by LIBS. Results showed that the Na-release at the devolatilization, char, and ash stages can be distinguished by FES. The higher Si/Al content in ash can suppress the Na-release at the ash stage. Moreover, FES method was extended to the measurement of Na-release in four industrial boiler furnaces of two Zhundong coal-fired power plants. Results showed the Na-release measured by FES can reflect the change of fuel and load, and both temperature and thermal radiation play key roles in Na-release in coal combustion.     

Experimental and modeling study on centimeter pine char combustion in fast-heating Macro TGA

Biomass energy is an important renewable resource, and thermochemical conversion, including pyrolysis and combustion, is one of the main methods of biomass energy utilization. In industrial reactors, the biomass particles will experience a fast heating (∼1000 °C/min) process during pyrolysis. The particle size of biomass applied in industry has a wide range (from millimeter to centimeter scale). The study of the reaction characteristics of biomass pyrolysis and combustion is helpful for optimizing furnace design and working condition selection. In this research, the combustion of centimeter-scale pine char was studied with a newly built fast-heating Macro Thermal Gravimetric Analyzer (Macro TGA). This Macro TGA is able to conduct the pyrolysis and combustion of large biomass samples (up to 40 mm) with a fast heating rate (∼1000 °C/min), which is able to reflect the working conditions in industrial-scale reactors such as grate furnaces and dual fluidized beds. This Macro TGA can measure the online sample weight, temperature and sample size simultaneously during pyrolysis and combustion experiments. The combustion characteristics of different sizes of pine chars were investigated at various temperatures and oxygen concentrations. A zero-dimensional model was established to predict the sample weight loss, temperature change and sample shrinkage during the pine char combustion process. Three kinetic parameters α, A and E were applied in the model, and the values of the kinetic parameters were optimized by a genetic algorithm. The model prediction and experimental results are consistent with each other. Compared with previous studies, this study developed a new experimental method to measure the reaction characteristics (including sample weight, temperature and size) of centimeter-scale biomass under similar pyrolysis and combustion reaction conditions compared to industrial reactors, and a zero-dimensional model was established to describe the pine char combustion process.     

An improved model of fine particulate matter formation coupling the mechanism of mineral coalescence and char fragmentation during pulverized coal combustion

An improved model of fine particulate matter formation coupling the mechanism of mineral coalescence and char fragmentation under different pulverized coal combustion environments has been constructed. Firstly, based on the theoretical model of char fragmentation and percolation, the included minerals with different types and particle sizes are constructed in the model, and a three-dimensional char particle sub-model is established. And the type, content and particle size distribution of included minerals are introduced as input parameters by using computer controlled scanning electron microscopy (CCSEM) technology. All of the above makes it more in line with the actual distribution of the included minerals. Then a sub-model of char fragmentation is built based on the sub-model of the char particle. And considering the influence of char combustion reaction on the particle formation process and melting characteristics of included minerals, a sub-model of mineral melting coalescence under different combustion environments is established. Finally, based on this improved model, we compared the calculation results with the experimental data and the calculation results of the traditional model. Fully considering the process of mineral coalescence and char fragmentation, which contains the characteristics of different included minerals, the results show that the newly established model has a good fitting effect for the experiment and is closer to the actual process of char particle combustion to generate particles. By the new model, the influence of the factors (mineral content, particle size distribution and porosity) on the formation of particulate matter is preliminarily analyzed.     

多孔焦炭燃烧特性的模型构建及数值模拟

焦炭燃烧在固体含碳燃料燃烧进程中占有主导地位,常规燃烧温度范围内(1273～1700 K)的焦炭燃烧过程研究及其模型化对于燃烧设备的设计和优化具有重要的意义。本文根据实际炉内的炭粒燃烧情况,将焦炭燃烧的模拟过程分解成几个环节分别进行研究,即热解后焦炭的初始化学反应活性、焦炭燃烧中化学活性变化、外部氧的扩散对于内孔燃烧的影响,并给出了相关过程的模型计算式。通过与已有管式炉实验结果的比较,新模型的预测结果能较好地反映焦炭的真实燃烧状况。与目前常用的焦炭燃烧模型相比,本模型具备一定的燃料通用性,计算负荷低且能保持相当的预测精度,可耦合到大型燃烧计算程序之中,更为有效地指导实际燃烧设备的优化设计。     

Characterization of high heating-rate chars from alternative fuels using an electrodynamic balance

Important advantages in the use of alternative and renewable fuels (CO₂ reduction in the atmosphere, recovery of energy from wastes, limited SO_x, NO_x and heavy metal emissions) can be obtained only by solving technological and economical problems that make direct combustion of such fuels impractical. This is possible after a detailed investigation to determine the most important features of these materials in all steps of the thermal process. At present, few data can actually be found for the char properties of these fuels. Nevertheless, the knowledge of properties of chars (especially after severe devolatilization) is crucial for both modeling purposes (reactivity, kinetics of combustion and gasification, morphology variations, composition, and fate of pollutant precursors) and practical applications (boiler efficiency, ash deposition, and condensation causing fouling and slagging problems).This work deals with the characterization of chars from different classes of materials (biomasses, waste, and low and high volatile matter (VM) coals) obtained after a devolatilization performed in severe thermal conditions, i.e., high temperature and high heating rate. A methodological approach is developed, applied, and discussed, using an electrodynamic balance that is a versatile analyzer for the study of properties of single levitated particles. The specific heat, size, and shape distribution, and density variation between the char and the parent material are evaluated for all materials. Scanning electron microscopy (SEM) analysis is also carried out to investigate morphological variations and support the major results obtained with the electrodynamic analyzer.