灰对煤焦燃烧的动力学研究

基于表观动力学灰膜缩核模型,本文发展并利用耦合的灰膜与灰渗透本征动力学模型,详细研究焦炭颗粒燃烧特性。氧化反应与气化反应耦合能够高精度预测煤焦颗粒燃烧特性。随灰膜形成比例下降,焦炭颗粒燃烧温度升高,碳燃尽时间缩短;当碳转化率低于80%时,碳转化率主要受灰膜影响,灰渗透影响甚微;但当碳转化率大于80%时,灰膜与灰渗透同时起作用。     

惰性颗粒流化床中低浓度煤层气燃烧特性实验

采用实验的方法,在鼓泡流化床燃烧装置中研究了低浓度煤层气在床内的流动和燃烧特性,考察了床层温度、气体浓度、流化风速及床料颗粒特性等操作条件变化对甲烷转化率和燃烧产物的影响。研究表明:床层温度升高,甲烷转化率显著增加;增加流化风速及进气甲烷浓度,甲烷转化率减小;颗粒粒径增加,甲烷转化率增加;CO排放浓度随床层温度的升高先增加后降低,并在床层温度约850℃时达到其最大峰值,沿流化床轴向高度CO的排放浓度先增加后降低,呈钟型分布。     

煤焦O_2/CO_2燃烧反应性及结构演化的分子模拟研究

本文通过自编程序Fringe3D和Vol3D构建了具备一定孔隙结构特征的大尺度煤焦分子模型(碳原子数~40000),通过简化的分子模拟方法编程实现了煤焦O_2/CO_2燃烧微观反应过程的模拟。模拟结果表明:随着燃烧反应的进行,煤焦结构逐渐"缩核"变小,而煤焦结构尺寸的变化主要发生在燃烧后期。随着碳转化率的增大,低活性碳原子的数量逐渐减少,而高活性碳原子的数量先增加后减少。与空气燃烧相比,煤焦在O_2/CO_2气氛下的燃烧过程明显延迟,而煤焦比表面积的改变对煤焦反应性的变化有紧密关联。     

煤焦破碎成灰模型研究

本文从颗粒破碎的角度,建立了燃烧过程中单颗煤焦的逾渗破碎及其成灰模型,并深入研究了初始大孔隙率对颗粒破碎程度以及残灰粒径分布的重要影响。模拟结果再现了无大孔存在(φ=0)情况下,单颗煤焦生成单颗残灰的实验事实;研究结果还表明,在所考察的取值范围内,初始大孔隙率φ越大,煤焦颗粒破碎越剧烈,燃烧前期的破碎程度也随之升高,同时,φ越大,燃烧过程中单颗煤焦生成残灰的数目越多,平均粒径越小,而且残灰主要集中在粒径较小的范围内。     

煤粉燃烧炉内细颗粒物沿程演化特性模拟

本文针对微米及亚微米细颗粒物在煤粉自维持燃烧高温一维炉中的沿程演化特性进行了定量模拟。从高温火焰区到焦炭燃烧区,利用聚并机理和碳烟氧化模型计算了细颗粒物浓度的粒径分布(PSD)变化,表明碳烟氧化是焦炭燃烧区颗粒浓度分布变化的主要因素,仅聚并作用无法生成PM_(0.1)以上颗粒。并通过预设碳烟份额得到与实验值吻合较好的焦炭燃烧区出口颗粒浓度分布曲线。     

烟煤煤焦高温热失活特性

通过热重(TG)实验研究了不同温度和时间下烟煤煤焦反应性的变化特性,辅助拉曼光谱对烟煤煤焦反应性变化的原因进行了分析,得到了煤焦热失活动力学模型。结果表明,随着热处理温度(HTT)和时间的增加,煤焦的反应性逐渐降低;煤焦的有序化程度随着热处理温度的升高而加深,说明煤焦在高温热处理下结构趋于稳定,是煤焦失活的主要原因.改进并用实验值验证了Salatino等人提出的煤焦热失活动力学模型,得到了可以用于CFD软件的煤焦热失活动力学模型.     

基于赤铁矿载氧体的污泥化学链燃烧研究

基于污泥处置技术的减容化、无害化、稳定化和资源化的目的,本文首次采用化学链燃烧技术来处置污泥,实验基于赤铁矿载氧体在1 kW_(th)串行流化床上开展。研究了燃料反应器温度对污泥燃烧特性的影响,并对比了淮北无烟煤和污泥化学链燃烧特性的差异,以及考察了赤铁矿长期运行的物化性能。实验结果表明,在本实验的工况下,没有焦炭随载氧体进入到空气反应;随着燃料反应器温度的增加,污泥和煤的碳转化率均增加,但污泥的碳转化率要高于煤;同时,水蒸气的加入可提高污泥的碳转化率,但水蒸气的量对其影响较小;赤铁矿在长时间运行中,体现了良好的反应以及抗烧结性能。     

移动床内合成气化学链燃烧反应的实验研究

近年来,全球变暖带来的一系列问题,减少温室气体CO_2排放已成为全世界关注的焦点。化学链燃烧技术作为一项有前途的CO_2分离技术,已成为各国研究的热点。本文搭建了移动床反应器实验台,对以烧结矿为载氧体的合成气化学链燃烧反应过程进行了研究,获得了稳态工况下气体浓度随床高的变化趋势,并分析了反应温度、烧结矿颗粒粒径、气固流量比对反应的影响。结果表明:自移动床底部到顶部,还原气体浓度逐渐下降;随着温度的升高,合成气转化率有明显的提高;烧结矿载氧体颗粒粒径减小,合成气转化率增加;气固流量比的减小可提高合成气转化率。     

激光消光法测量RP-3航空煤油富油燃烧的碳烟产率

利用由He-Ne激光器、单色仪、光电倍增管(PMT)和数字示波器等组成的光学平台,采用激光消光法测量了RP-3航空煤油高温裂解和富油燃烧的碳烟产率。实验条件:RP-3航油摩尔浓度0.25%和0.5%,压力约2和4atm,高温裂解和当量比20.0,10.0,5.0,温度1 700~2 273K。结果显示裂解条件下碳烟产率随温度变化呈高斯分布,随着压力或浓度的增大,碳烟产率增大;富油燃烧条件下当量比越低,碳烟产率越低。本文结果为研究发动机内碳烟颗粒物排放及碳烟形成机理提供了实验依据。     

热处理对煤焦气化和燃烧反应性的影响

利用非等温热重法研究了不同温度下制得的褐煤煤焦CO_2气化和燃烧反应动力学,得到了各反应的反应性指数、活化能、反应速率常数等动力学参数。结果表明,煤焦两种反应的反应性指数、活化能均随着热处理温度的升高而增大,即煤焦的反应性随着热处理温度的升高而减小。矿物质对煤焦的两种反应均具有催化作用,该作用随着热处理温度的升高而减小。煤焦两种反应的反应速率常数k随热处理温度升高显示出不同的变化趋势,反映了煤焦物理化学特性对气化和燃烧反应影响的差异和两种反应动力学过程的不同。     

An intrinsic kinetics model to predict complex ash effects (ash film,dilution, and vaporization) on pulverized coal char burnout in air (O2/N2) and oxy-fuel (O2/CO2) atmospheres

During coal combustion, char chemical reaction is the slowest step, particularly in the last burnout stage, where the char consists of small amounts of carbon in a predominant ash framework. Existing kinetics models tend to deviate from experimental measurements of late char burnout due to the incomplete treatment of ash effects. Ash can improve pore evolution through vaporization, hinder oxygen transport by forming an ash film, and reduce active carbon sites and available surface per unit volume by penetrating into the char matrix. In this work, a sophisticated kinetics model, focusing on these three ash evolution mechanisms (ash vaporization, ash film, and ash dilution) during pulverized coal (PC) char combustion, is developed by integrating them into a thorough mechanistic picture. Further, a detailed comparison of the three distinct ash effects on PC char conversion during air (O₂/N₂) and oxy-fuel (O₂/CO₂) combustion is performed. For the modeled coal, the mass of ash vaporization is approximate 3 orders less than the mass of ash remaining, which participates in ash dilution and ash film formation, both in O₂/N₂ and O₂/CO₂ atmospheres. The influence of these phenomena on burnout time follows the order: ash dilution > ash film > ash vaporization. The influence of ash vaporization on burnout time is minor, but through interactions with the ash dilution and ash film forming processes it can have an impact at high extents of burnout, particularly in O₂/CO₂ atmospheres. In O₂/N₂ atmospheres the residual ash predominately exists as an ash film, whereas it mainly exists as diluted ash in the char matrix in O₂/CO₂ atmospheres. The residual ash particle is encased by a thick film when the ash film forming fraction is high (low ash dilution fraction). These results provide in-depth insights into the conversion of PC char and further utilization of the residual ash.     

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.     

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.     

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.     

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。     

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.     

The influence of thermal annealing on oxygen uptake and combustion rates of a bituminous coal char

The effect of thermal annealing on the combustion reactivity of a bituminous coal char has been investigated with a focus on the role of the formation of surface oxides by oxygen chemisorption. The combined use of thermogravimetric analysis and of analysis of the off-gas during isothermal combustion of char samples enabled the determination of the rate and extent of oxygen uptake along burn-off. Combustion was carried out at temperatures between 350 and 510 °C. Char samples were prepared by controlled isothermal heat treatment of coal for different times (in the range between 1 s and 30 min) at different temperatures (in the range 900–2000 °C). Results indicate that oxygen uptake is extensive along burn off of chars prepared under mild heat treatment conditions. The maximum oxygen uptake is barely affected by the combustion temperature within the range of combustion conditions investigated. The severity of heat treatment has a pronounced effect on char combustion rate as well as on the extent and rate at which surface oxides are built up by oxygen chemisorption. Chars prepared under severe heat treatment conditions show negligible oxygen uptake and strongly reduced combustion rates. Altogether it appears that a close correlation can be established between the extent and the accessibility of active sites on the carbon surface and the combustion rate. Despite the investigation has been carried out at temperatures well below those of practical interest, results provide useful insight into the relationship existing between thermal annealing, formation of surface oxide and combustion reactivity which is relevant to the proper formulation of detailed kinetic models of char combustion.     

Mineral associations in coal and their transformation during gasification

The principle aim of this investigation was to determine the effect that minerals and mineral associations in dense medium coal fractions have on the ash fusion temperature (AFT) of coal, where the mineral matter associated with coal undergoes transformations during gasification. Samples from three coal sources used by Sasol for gasification were acquired and a comprehensive characterisation on all dense medium fractions was conducted, including proximate analyses, AFT, ash oxide analyses, XRD and Mössbauer spectroscopy. From the proximate analyses, the ash content was the highest for the higher density fractions, with an accompanying decrease in fixed carbon content, consistent with the XRD and Mössbauer analyses. From the ash oxide analyses, it was evident that at higher relative densities more Fe₂O₃ and SiO₂ were present than in the lower density samples. From XRD analyses, the low density fractions contained calcite and dolomite. Pyrite and quartz were found in the higher density fractions whereas kaolinite occurred in all density separated fractions. From the different techniques it follows that with the Fe-content high in high density fractions, the AFT was low. When Ca and other basic oxide levels were abundant in low density fractions, the AFT was low and when the SiO₂/Al₂O₃ ratio was high in high density fractions the AFT increased.     

Kinetics of coal char gasification in a carbon dioxide medium

Solid fuel samples with different carbon contents are gasified by successively subjecting to pyrolysis in argon and oxidation in carbon dioxide at various temperatures to determine the rate of the chemical reactions and the activation energy required for simulating and optimizing the operation of gas generators. The samples were prepared from bituminous coal, lignite, and anthracite of the Kuznetsk and Kansk-Achinsk coal basins. The gasification of coal char samples in a carbon dioxide medium at 900–1200°C is analyzed by thermogravimetry. The temperature dependences of the weight change rate and gasification time of coal char samples are measured and used to calculate the preexponential factor and activation energy of the carbon oxidation reaction. It is found that, with increasing oxidizing medium temperature from 900 to 1200°C, the gasification time of the coal char samples obtained from anthracite and bituminous coal decrease 8- and 22-fold, respectively. A physicomathematical model of coal char gasification in a fixed bed, with the oxidizing gas diffusing through the ash layer formed, is proposed.     

Prediction of particle sticking efficiency for fly ash deposition at high temperatures

The tendency of ash particles to stick under high temperatures is dictated by the ash chemistry, particle physical properties, deposit surface properties and furnace operation conditions. A model has been developed in order to predict the particle sticking efficiency for fly ash deposition at high temperatures. The model incorporates the particle properties relevant to the ash chemistry, particle kinetic energy and furnace operation conditions and takes into consideration the partial sticking behaviour and the deposit layer. To test the model, the sticking behaviours of synthetic ash in a drop tube furnace are evaluated and the slagging formation from coal combustion in a down-fired furnace is modelled. Compared with the measurements, the proposed model presents reasonable prediction performance on the particle sticking behaviour and the ash deposition formation. Through a sensitivity analysis, furnace operation conditions (velocity and temperature), contact angle and particle size have been found to be the significant factors in controlling the sticking behaviours for the synthetic ash particles. The ash chemistry and furnace temperature dictate the wetting potential of the ash particles and the melting ability of the deposit surface; particle size and density not only control the particle kinetic energy, but also affect the particle temperature. The furnace velocity condition has been identified as being able to influence the selective deposition behaviour, where the maximum deposition efficiency moves to smaller particles when increasing the gas velocity. In addition, the thermophoresis effect on the arrival rate of the particles reduces with increasing the gas velocity. Further, increasing the melting degree of the deposit layer could greatly enhance the predicted deposition formation, in particular for the high furnace velocity condition.