Char characteristics and particulate matter formation during Chinese bituminous coal combustion

The characteristics of char particles and their effects on the emission of particulate matter (PM) from the combustion of a Chinese bituminous coal were studied in a laboratory-scale drop tube furnace. The raw coal was pulverized and divided into three sizes, <63, 63–100, and 100–200 μm. These coal samples were subjected to pyrolysis in N₂ and combusted in 20 and 50% O₂ at 1373, 1523, and 1673 K, respectively. Char samples were obtained by glass fiber filters with a pore size of 0.3 μm, and combustion-derived PM was size-segregated by a low pressure impactor (LPI) into different sizes ranging from 10.0 to 0.3 μm. The characteristics of char particles, including particle size distribution, surface area, pore size distribution, swelling behavior and morphology property, were studied. The results show that, coal particle size and pyrolysis temperature have significant influence on the char characteristics. The swelling ratios of char samples increase with temperature increasing from 1373 to 1523 K, then decrease when the temperature further increases to 1623 K. At the same temperature, the swelling ratios of the three size fractions are markedly different. The finer the particle size, the higher the swelling ratio. The decrease of swelling ratio at high temperature is mainly attributed to the high heating rate, but char fragmentation at high temperature may also account for the decrease of swelling ratio. The supermicron particles (1–10 μm) are primarily spherical, and most of them have smooth surfaces. Decreasing coal particle size and increasing the oxygen concentration lead to more supermicron-sized PM formation. The influence of combustion temperature on supermicron-sized PM emission greatly depends on the oxygen concentration.     

Mechanism on the contribution of coal/char fragmentation to fly ash formation during pulverized coal combustion

In this paper, the correlations between coal/char fragmentation and fly ash formation during pulverized coal combustion are investigated. We observed an explosion-like fragmentation of Zhundong coal in the early devolatilization stage by means of high-speed photography in the Hencken flat-flame burner. While high ash-fusion (HAF) bituminous and coal-derived char samples only undergo gentle perimeter fragmentation in the char burning stage. Simultaneously, combustion experiments of two kinds of coals were conducted in a 25?kW down-fired combustor. The particle size distributions (PSDs) of both fine particulates (PM_1-10) and bulk fly ash (PM₁₀₊) were measured by Electrical Low Pressure Impactor (ELPI) and Malvern Mastersizer 2000, respectively. The results show that the mass PSD of residual fly ash (PM₁₊) from Zhundong coal exhibits a bi-modal shape with two peaks located at 14?µm and 102?µm, whereas that from HAF coal only possesses a single peak at 74?µm. A hybrid model accounting for multiple-route ash formation processes is developed to predict the PSD of fly ash during coal combustion. By incorporating coal/char fragmentation sub-models, the simulation can quantitatively reproduce the measured PM₁₊ PSDs for different kinds of coals. The sensitivity analysis further reveals that the bi-modal mass distribution of PM₁₊ intrinsically results from the coal fragmentation during devolatilization.     

Mechanisms of the central mode particle formation during pulverized coal combustion

Ash particles produced from pulverized coal combustion are considered to be tri-modally distributed. These include the well-known ultrafine and coarse modes, and a central mode that is less reported but attracts increasing attention. This work presents a preliminary study on the formation mechanisms of the central mode particles during pulverized coal combustion. Experiments of four sized and density-separated coal samples were carried out in a laboratory drop-tube furnace under various controlled conditions. Experimental data show that the ash particle size distributions have an evident central mode at 4 μm for all coal samples. Increasing combustion temperature leads to an increase in the central mode particle formation, which is thought to be due to enhanced char fragmentation. The small-size coal sample produces a larger amount of the central mode particles, reasonably due to abundant fine particles in the parent coal sample. Under similar combustion conditions, both the Heavy (>2.0 g/cm³) and Light (<1.4 g/cm³) coal fractions produce a central mode, indicating that not only the included minerals but also the excluded minerals contribute to the formation of the central mode particles.     

Evaluation of char combustion models: measurement and analysis of variability in char particle size and density

Char samples representing a range of combustion conditions and extents of burnout were obtained from a well-characterized laminar flow combustion experiment. Individual particles from the parent coal and char samples were characterized to determine distributions in particle volume, mass, and density at different extent of burnout. The data were then compared with predictions from a comprehensive char combustion model referred to as the char burnout kinetics model (CBK). The data clearly reflect the particle-to-particle heterogeneity of the parent coal and show a significant broadening in the size and density distributions of the chars resulting from both devolatilization and combustion. Data for chars prepared in a lower oxygen content environment (6% oxygen by vol.) are consistent with zone II type combustion behavior where most of the combustion is occurring near the particle surface. At higher oxygen contents (12% by vol.), the data show indications of more burning occurring in the particle interior. The CBK model does a good job of predicting the general nature of the development of size and density distributions during burning but the input distribution of particle size and density is critical to obtaining good predictions. A significant reduction in particle size was observed to occur as a result of devolatilization. For comprehensive combustion models to provide accurate predictions, this size reduction phenomenon needs to be included in devolatilization models so that representative char distributions are carried through the calculations.     

The effect of pelletization on the attrition of wood under fluidized bed combustion and gasification conditions

This work reports on a study, carried out in a lab-scale fluidized bed apparatus, on fragmentation and attrition of two biomass fuels, namely wood chips and wood pellets, under both combustion and gasification conditions. The aim was to highlight the effect of their different mechanical strength on the fuel particle size distribution and overall carbon conversion. Primary fragmentation tests showed that for wood pellets limited fragmentation occurred during devolatilization, with a fragmentation probability around 30% and particle multiplication factor of 1.4. On the contrary, wood chips were subject to extensive fragmentation as witnessed by large values of the particle multiplication factor and of the fragmentation probability.Results of char attrition experiments carried out under inert, combustion and gasification conditions showed that the carbon loss by elutriation is critical only during gasification, especially for the wood chips char. A gasification-assisted attrition mechanism was proposed to explain the experimental results, similar to the well known combustion-assisted attrition patterns already documented for coal under oxidizing conditions. The higher mechanical strength of the wood pellets appears to be beneficial for reducing carbon elutriation and for obtaining a higher carbon conversion.     

褐煤热解与燃烧时矿物转化和细灰形成的CCSEM研究

在沉降炉中进行了一种典型中国褐煤的热解与燃烧实验,热解气氛为N2,燃烧气氛为O₂/N₂=21:79,采用CCSEM分析原煤、煤焦与煤灰。CCSEM分析结果表明,铁氧化物、石英、黄铁矿、伊利石和高岭土是煤中主要的矿物成分,同时也是主要的外在矿成分,褐煤中57.26%的矿物粒径小于10μm。在热解与燃烧过程中,煤中主要矿物发生了明显转化。富Si矿物和硅铝酸盐在热解和燃烧过程中可能发生了破碎;而富Fe矿物部分明显破碎生成细小矿物,部分外在矿直接转化,未发生明显破碎。细灰少量来自于细小富硅矿、石英和铁氧化物等矿物的直接转化,70%以上的细灰由Ca、Fe含量很高的混合硅铝酸盐组成。     

PM10 formation during the combustion of N2-char and CO2-char of Chinese coals

The formation of PM₁₀ (particles less than or equal to 10 μm in aerodynamic diameter) during char combustion in both air-firing and oxy-firing was investigated. Three Chinese coals of different ranks (i.e., DT bituminous coal, CF lignite, and YQ anthracite) were devolatilized at 1300 °C in N₂ and CO₂ atmosphere, respectively, in a drop tube furnace (DTF). The resulting N₂-chars and CO₂-chars were burned at 1300 °C in both air-firing (O₂/N₂ = 21/79) and oxy-firing (O₂/CO₂ = 21/79). The effects of char properties and combustion conditions on PM₁₀ formation during char combustion were studied. It was found that the formation modes and particle size distribution of PM₁₀ from char combustion whether in air-firing or in oxy-firing were similar to those from pulverized coal combustion. The significant amounts of PM_0.5 (particles less than or equal to 0.5 μm in aerodynamic diameter) generated from combustion of various chars suggested that the mineral matter left in the chars after coal devolatilization still had great contributions to the formation of ultrafine particles even during the char combustion stage. The concentration of PM₁₀ from char combustion in oxy-firing was generally less than that in air-firing. The properties of the CO₂-chars were different from those of the N₂-chars, which was likely due to gasification reactions coal particles experienced during devolatilization in CO₂ atmosphere. Regardless of the combustion modes, PM₁₀ formation in combustion of N₂-char and CO₂-char from the same coal was found to be significantly dependent on char properties. The difference in the PM₁₀ formation behavior between the N₂-char and CO₂-char was coal-type dependent.     

Fragmentation of pulverized coal in a laminar drop tube reactor: Experiments and model

Fragmentation during pulverized coal particles conversion shifts the particle size distribution of the fuel towards smaller particle sizes, affecting both conversion rates and heat release. After pyrolysis of a high volatiles Colombian coal in CO₂ atmosphere in a drop tube reactor at 1573?K, solid carbonaceous particles of different size, from 100?µm of the particle feed down to the nanometric size, have been observed. A fragmentation model has been used to predict the fate of Colombian coal particles under the experimental conditions of the drop tube experiment and predict the particle size distribution (PSD). Model and experimental results are in very good agreement and indicate that in the DTR experiment the coal underwent almost complete pyrolysis and that fragmentation generated a 36?wt% population of particles with size close to 30?µm. The close match between the PSDs obtained from experiments and from the fragmentation model is an important novelty. It demonstrates that fragmentation occurs not only under fluidized bed conditions but also under the conditions of pulverized coal combustion. Experimentalists are warned against the fact that the fine particulate sampled at the outlet of laminar flow reactors and boilers is not always composed of soot only. Char fragments can be misidentified as soot. The implementation of fragmentation submodels in pulverized fuel combustion and gasification codes is highly recommended.     

Effect of water vapour on particulate matter emission during oxyfuel combustion of char and in situ volatiles generated from rapid pyrolysis of chromated-copper-arsenate-treated wood

This paper reports the effect of water vapour on particulate matter (PM) during the separate combustion of in situ volatiles and char generated from chromated-copper-arsenate-treated (CCAT) wood at 1300 °C. Combustion of in situ volatiles produces only PM with aerodynamic diameter?<1?µm (i.e., PM₁), dominantly PM with aerodynamic diameter?<0.1?µm (i.e., PM_0.1). Water vapour could significantly enhance the nucleation, coagulation and condensation of fine particles and reduce the capture of Na and K by the alumina reactor tube via reduced formation of alkali aluminates, leading to increases in both yield and modal diameter of PM_0.1. Water vapour could also enhance char fragmentation hence increase the yield of PM with aerodynamic diameter between 1 and 10?µm (i.e., PM_1–10) during char combustion. For trace elements, during in situ volatiles combustion, volatile elements (As, Cr, Ni, Cu and Pb) are only presented in PM₁ and water vapour alters the particle size distributions (PSDs) but has little effect on the yields of these trace elements. During char combustion, As, Cr, Cu and Ni are present in both PM₁ and PM_1–10 while the non-volatile Mn and Ti are only present in PM_1–10. Increasing water vapour content increases the yields of As, Cr, Cu, Ni, Mn and Ti in PM_1-10 due to enhanced char fragmentation. During char combustion, water vapour also originates less oxidising conditions locally for enhancing As release, promotes the generation of gaseous chromium oxyhydroxides and inhabits the production of NiCl₂ (g), leading to increased yields of As and Cr and decreased yield of Ni in PM_0.1.     

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。     

Pressurized oxy-fuel combustion of a char particle in the fluidized bed combustor

Pressurized oxy-fuel combustion of coal in fluidized bed (FB) holds the potential to realize low-cost CO₂ capture. However, the fundamental study in this manner is still rare due to the difficult access to the pressurized oxy-FB combustion tests. In this work, the experimental study of single char combustion was firstly conducted in a visualized pressurized FB combustor under various operating conditions. Then an experimentally verified particle-scale char combustion model was developed to reveal the dependence of char combustion on parameters. Results showed that the char conversion was accelerated with the increase of pressure, mainly due to the high oxygen diffusion and char gasification. The gasification played a non-negligible role in pressurized oxy-fuel combustion, especially under high oxygen concentration and bed temperature. Increasing oxygen concentration and bed temperature not only promotes the char oxidation rate and particle temperature, but also increases the gasification rate and the share of char conversion via gasification, resulting in shortening the burnout time of char. In addition, a higher fluidization number lowered both the burnout time and peak temperature of char particle, due to the simultaneous improvement of mass and heat transfer. The influences of char size and fluidization number on char gasification conversion ratio are very weak. In addition, the quantitative analysis of the influence of different operating parameters on the combustion process was obtained by model sensitivity analysis.     

Modelling the length distribution of etched tracks taking into account fragmentation due to partial annealing

Fission track length measurements on apatite minerals are of great interest in thermo-chronology studies. RBS analyses on Durango apatites irradiated by Krypton ions have previously shown the progressive fragmentation of tracks by annealing. This study made for different irradiation energies corresponding to those of uranium fission fragments has been completed by TEM and AFM on etched tracks. In all cases, segmentation figures have been observed, that clearly necessitates to introduce fragmentation of latent tracks to model the length distribution of uranium etched fission tracks. This presentation concerns the case of a homogeneous population of tracks with partial amorphization. The next step will consist in considering multiple sub-populations with different segmentation rates. This algorithm is a new aspect to be included in our model, which already takes into account diffusion and crystallography in the track etching process.     

Modeling of the submicron particles formation and initial layer ash deposition during high temperature oxy-coal combustion

The future use of coal as a fuel for power generation in the US depends on the availability of financially viable technologies for capture and storage of CO₂ emissions from power plants. Key second-generation candidates for CO₂ capture include high temperature and pressurized oxy-firing of coal, which has the potential to increase efficiency, lower capital costs, avoid air ingress and reduce oxygen requirements. However, unquantified challenges, such as flame behavior, heat transfer, ash transformation, ash deposition and char oxidation, still exist for those technologies. This study specifically focuses on the formation of submicron particles and initial layer ash deposition during high temperature oxy-coal combustion. Previous work has shown that the initial layer deposits are mainly formed of submicron size ash aerosols transported by thermophoresis. Unfortunately, the importance of submicron particle deposition has not received much attention, probably due to the insignificant deposit mass and difficulty in prediction of the submicron particles formation. In this work, models including mineral matter vaporization model, scavenging model and deposition model are developed and applied into a three-dimensional CFD framework to predict the submicron particles formation and subsequent initial layer deposits formation. The model results are comparable to experimental data. The merits of this work are that it has led to the development of a novel approach to predict both submicron particle formation and initial layer ash deposition during oxy-coal combustion.     

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.     

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.     

Analysis of model dimensionality,particle shrinkage,boundary layer reactions on particle-scale modelling of biomass char conversion under pulverized fuel combustion conditions

In this work, the effects of model dimensionality, particle shrinkage, and boundary layer reactions on particle-scale modelling of biomass char conversion under pulverized fuel combustion conditions have been analysed by using six models: zero-dimensional models with constant particle size (0D_Cons) or shrinking particle size (0D_SPM), one-dimensional models with/without considering particle shrinkage (1D_Cons/1D_SPM), and 1D_Cons and 1D_SPM with considering boundary layer reactions (1D_Cons_BH and 1D_SPM_BH). A comparison with existing experimental data shows that the 1D_SPM_BH model with consideration of intra-particle heat and mass transfer, particle shrinkage, and boundary layer reactions is an appropriate model to describe biomass char conversion over a wide range of conditions. The 0D_Cons model is a good approximation for the conditions of small particle size (< 1 mm) at 1273–1473 K, but overestimates the char conversion rate for larger biomass char particle or at high temperatures (regime III). The 0D_SPM model gives a reasonable prediction on char conversion time but predicts a larger contribution of reaction between char and O₂ as compared to the 1D_SPM_BH model. The consideration of intra-particle heat and mass transfer in particle-scale modelling (1D_Cons and 1D_SPM) is beneficial to improving the model prediction of char conversion time and the contributions of char oxidation and gasification reactions. The boundary layer reactions have a significant effect on the prediction of char conversion for large particles (> 1 mm) and high temperatures (> 1473 K). An implication for the selection of a particle-scale model in CFD modelling is also given.     

煤焦燃烧过程中的亚观和微观形态及反应机理

通过FESEM和EBSP对煤粉在TGA、DTF和电站锅炉内燃烧过程中的亚观和微观形态及碳的含量变化的研究表明:炭的形态可分为5类:薄壁网架炭、厚壁网架炭、浅孔实体炭、实体炭和含碳矿物;同一煤样同一温度条件下炉内炭比TGA和DTF中的炭具有更大的反应比表面积;炉内炭的表面含碳量变化不大,不存在低温反应器的表面灰壳,因此,应用球形灰壳理论预报炉内煤粉的燃烧速率是值得怀疑的;亚观形态与微观形态间不存在几何分形上的自相似性.     

A full spectrum k-distribution based non-gray radiative property model for unburnt char

By using the concept of weighted sum of four gray particles and spectrum k-distribution (WSGP-SK), a non-gray radiative property model for unburnt char particles is developed. Based on the carbon burnout kinetic model for structure during oxidation, and the linear mixed approximation theory for complex index of refraction, spectral radiative properties of unburnt char particles are first calculated as function of the burnout ratio by Mie theory. Referring to the full spectrum k-distribution model, k-distribution is applied to reorder absorption and scattering efficiencies of particles. Then, weighting factors and efficiency factors of the non-gray radiative property model are directly obtained from Gaussian integral points of k-distribution. The model is validated against the benchmark solutions of line-by-line (LBL) model. Maximum relative errors of this model are 3% and 15% for radiative heat fluxes and source terms in non-isothermal inhomogeneous particulate media, respectively. The assumption of linearly varying radiative properties with burnout ratio (Lockwood et al. 1986) will result in a predicted deviation of 53% for radiative source terms. Results also show that this non-gray model is remarkably better than the Planck mean method. Moreover, a satisfactory comparison with LBL solutions is achieved in the gas and particle mixture by combining the non-gray WSGG-SK model (Guo et al. 2015). As a radiation sub-model, this non-gray radiative property model can significantly improve prediction accuracy of radiative heat transfer in oxy-fuel combustion.     

Studies on aluminum powder combustion in detonation environment

The combustion mechanism of aluminum particles in a detonation environment characterized by high temperature (in unit 10³ K), high pressure (in unit GPa), and high-speed motion (in units km/s) was studied, and a combustion model of the aluminum particles in detonation environment was established. Based on this model, a combustion control equation for aluminum particles in detonation environment was obtained. It can be seen from the control equation that the burning time of aluminum particle is mainly affected by the particle size, system temperature, and diffusion coefficient. The calculation result shows that a higher system temperature, larger diffusion coefficient, and smaller particle size lead to a faster burn rate and shorter burning time for aluminum particles. After considering the particle size distribution characteristics of aluminum powder, the application of the combustion control equation was extended from single aluminum particles to nonuniform aluminum powder, and the calculated time corresponding to the peak burn rate of aluminum powder was in good agreement with the experimental electrical conductivity results. This equation can quantitatively describe the combustion behavior of aluminum powder in different detonation environments and provides technical means for quantitative calculation of the aluminum powder combustion process in detonation environment.     

Use of elemental size distributions in identifying particle formation modes

The chemical composition of particles generated during pulverized coal combustion is the consequence of their formation processes. This work aims to use the size resolved elemental composition of coal-derived particles to identify their formation modes. A size-classified bituminous coal is burnt in a laboratory drop tube furnace at 1150, 1250, and 1350 °C, respectively. The elemental composition of the size-segregated particles from coal combustion is analyzed and the total mass fraction size distributions of Si and Al are obtained. Three particle formation modes are observed in these distribution profiles. The coarse mode has the highest value of the total mass fraction of Si and Al while the ultrafine mode has the lowest one. The total mass fraction of Si and Al in these two modes is nearly independent of particle size. It is believed that the coarse mode is formed by the mineral coalescence mechanism and the ultrafine mode by the vaporization–condensation mechanism. The difference in the total mass fraction of Si and Al between the central mode and the other two indicates that the central mode is formed by different mechanisms. Based on the observation that the total mass fraction of Si and Al in this mode increases with increasing particle size, heterogeneous condensation of vaporized species on existing fine residual ash particles is proposed to account for the formation of these particles. The study of the elemental composition of the three modes represented in five categories verifies the proposed formation mechanisms for them to some extent.