1000MW燃煤机组负荷变化对飞灰特性的影响

燃煤机组变负荷调峰运行是提高可再生能源消纳能力的重要举措，但会对燃烧过程及系统产生重要影响。飞灰特性与锅炉结渣、除尘设备性能、颗粒物排放等密切相关，笔者研究了燃煤锅炉负荷变化对飞灰特性的影响规律，用于指导炉膛沾污结渣和颗粒物排放等相关问题的防控。针对1 000 MW燃煤锅炉，在60%和90%运行负荷下分别采集飞灰样品，利用先进的计算机自动控制扫描电镜(CCSEM)技术对飞灰化学和矿物成分、粒径分布以及形状特征进行深入表征，采用数字成像煤灰熔点分析仪对飞灰熔融温度进行分析，揭示了锅炉运行负荷变化对飞灰特性和熔融行为的影响。研究结果表明锅炉在不同运行负荷条件下飞灰化学成分相似。无机矿物元素交互作用是影响飞灰粒径分布的关键因素，低负荷运行工况下煤中含Ca和Fe的矿物与硅铝酸盐交互反应减弱，飞灰整体粒径分布向小粒径迁移，飞灰的D₅₀(小于该粒径的颗粒占50%)由约40μm减至约30μm。相比高负荷运行工况，低负荷运行工况下飞灰在炉膛中的熔融受抑制，熔融飞灰比例相比高负荷运行工况降低约10%,低负荷运行条件下燃烧温度降低是导致飞灰熔融比例降低的主要原因。     

粒度对煤灰熔融特性的影响及作用机理初探

利用计算机控制扫描电镜(CCSEM)和5E-AFⅡ型智能灰熔点测试仪分别研究了A和B两种典型煤样的矿物组成及粒径分布和煤灰熔融温度。结果表明,煤灰熔融温度随粒径增大呈直线上升的趋势,当粒径大于100μm时,煤灰流动温度大于1 450℃。A、B煤中高岭石、石英、硅铝酸钾、蒙脱石矿物均以中小颗粒的形式存在,方解石分别以小颗粒、粗大颗粒的形式存在,铁氧化物则反之,且内在、外在矿物颗粒分布存在非均一性,这些是导致煤灰熔融特性产生重大变化的根本原因。     

准东煤及其混煤燃烧与结渣特性

准东煤田是我国目前最大的整装煤田,煤质总体呈现中高水分、中高挥发分、低灰、低硫、低磷、中等热值、反应活性好等特点,是大规模煤化工、煤电气联产优质原料。但准东煤中较高的Na、Ca含量影响锅炉正常运行,限制了准东高钠煤的燃烧利用,目前电厂主要通过掺烧低钠煤方式加以利用。为考察准东煤及其混煤燃烧与结渣特性,在五彩湾电厂采集了准东煤(ZD)和乌东煤(WD)等2种原料煤。采用热重分析仪研究30%、50%和80%等不同配比下混煤燃烧特性,并分析响应配比下煤灰特性变化规律。结果表明,准东煤混煤燃烧的DTG曲线有2个特征峰。随准东煤配比增加,混煤燃烧TG和DTG曲线向低温区移动,DTG曲线特征峰更明显;混煤燃烧特征温度逐渐降低,最大燃烧速率与综合燃烧特性指数先降低后升高,混煤灰熔融温度逐渐降低。准东煤相对乌东煤具有较高的碱性氧化物和较低的酸性氧化物含量,准东煤配比越高相应的SO_3、CaO、Na_2O的含量越高结渣倾向性更强。但部分指标并不能准确预测结渣强弱,如准东煤硅铝比为1.67,而乌东煤硅铝比为3.02,依据硅铝比判断结渣倾向性与事实不吻合。另外,煤中CaO含量大于30%后继续增加则灰熔融温度升高,是准东煤比乌东煤具有更高灰熔融温度的原因,随准东煤配比增加,混煤灰熔融温度呈明显降低趋势。燃烧结渣与沾污倾向指标主要有基于煤灰成分和基于煤灰熔融温度的指标,总结分析以往结渣与沾污预测指标结合试验结果认为:基于煤灰成分的碱酸比以及基于煤灰熔融温度的特征温度差值(FT-DT)是判别准东煤及其混煤结渣与沾污倾向性的理想指标。     

准东煤高温燃烧过程中含钙矿物质的转化规律

采用3种萃取液（水、醋酸铵和盐酸）对准东煤进行逐级萃取实验,使用高温气氛炉对准东原煤及萃取后的煤样进行燃烧实验,使用电感耦合等离子体原子发射光谱仪和X射线衍射物相分析仪对萃取前后的固体煤样及燃烧后煤灰样品分别进行Ca元素分析和矿物检测。研究结果表明,准东煤中的钙元素主要以醋酸铵溶钙和盐酸溶钙形式存在。在燃烧过程中,准东煤中含钙矿物质与含硅、含铝矿物质反应生成硅钙石、斜硅钙石与钙铝石等;其中经水萃取后碱酸比减小,灰熔融温度升高,盐酸溶钙与含硅、含铝矿物质反应生成硅钙石、硅铝石等,不溶钙主要以稳定的硅铝酸盐形式存在。     

准东煤高温燃烧过程中含钙矿物质的转化规律

采用3种萃取液(水、醋酸铵和盐酸)对准东煤进行逐级萃取实验,使用高温气氛炉对准东原煤及萃取后的煤样进行燃烧实验,使用电感耦合等离子体原子发射光谱仪和X射线衍射物相分析仪对萃取前后的固体煤样及燃烧后煤灰样品分别进行Ca元素分析和矿物检测。研究结果表明,准东煤中的钙元素主要以醋酸铵溶钙和盐酸溶钙形式存在。在燃烧过程中,准东煤中含钙矿物质与含硅、含铝矿物质反应生成硅钙石、斜硅钙石与钙铝石等;其中经水萃取后碱酸比减小,灰熔融温度升高,盐酸溶钙与含硅、含铝矿物质反应生成硅钙石、硅铝石等,不溶钙主要以稳定的硅铝酸盐形式存在。     

Shell粉煤气化工艺煤灰熔融性探析

介绍Shell粉煤气化工艺中飞灰的形成过程及其特性,对煤灰的熔融性进行探析并提出稳定气化炉运行的操作建议。煤灰的熔融特性不仅与灰的成分有关,还与燃烧过程中灰中各成分之间的相互作用有关。灰熔融性温度主要取决于煤中的矿物组成、其氧化物的成分和配比及燃烧气氛等。     

O2/CO2燃烧对神华煤Ca和Fe交互反应影响

选用高Ca、高Fe含量的神华煤,在沉降炉系统中进行空气以及O₂/CO₂燃烧实验。利用X射线荧光探针(XRF)、X射线衍射仪(XRD)、先进计算机控制扫描电镜(CCSEM)分别对总灰元素、晶相组成以及主要矿物元素的共生特性进行深入表征。结果表明氧/燃料燃烧促进了Fe、Ca与其他矿物元素的交互反应,总灰中Fe在Fe-rich类矿物分布减少,而在铁铝硅酸盐(Fe-alsil),尤其是在Fe与Ca发生交互反应的Fe+Ca类矿物的分布增加,同时Ca也存在类似的分布规律。对总灰中Fe+Ca类矿物深入分析发现,氧/燃料燃烧条件下总灰中Fe+Ca类矿物结渣倾向更严重(Fe₂O₃/CaO摩尔比为0.5～3)。     

配煤对催化气化工艺中煤灰烧结行为影响研究

针对易结渣煤种,研究不同配煤方式对煤灰熔融特性的影响,在催化气化工况气氛下利用压差法烧结温度测定实验装置对各煤灰进行初始烧结温度测试,并结合X射线衍射(XRD)及Factsage热力学软件计算结果表征分析煤灰的相关物理和化学变化,推测灰中矿物质间的反应及矿物的转变,研究矿物质变迁规律,揭示缓解结渣机理。结果表明,通过将高灰熔点、高硅铝含量煤种同易结渣煤种混配可缓解易结渣煤种的结渣问题,同高灰熔点煤混合可有效提高易结渣煤种灰熔点;混煤工艺不同,对灰熔点及烧结温度影响各异,这主要与催化剂在煤质上分布、催化剂存在形式不同及其与不同煤种中矿物质作用不一有关。     

基于配煤矿物组成对煤灰熔融特性的影响研究

选取两淮煤矿具有代表性的2个煤样,分别与低灰熔融温度HM150煤进行相配,并通过X-射线衍射(XRD)对实验配煤煤样及其灰样中矿物组成以及相对百分含量作了分析,探讨了矿物种类及其相对百分含量对煤灰熔融温度的影响。研究得出:两淮煤其煤灰熔融温度过高的主要原因是其含有大量的高岭石和石英等矿物,石英、高岭石含量越高,煤灰熔融温度越高。配煤改善煤灰熔融温度的主要原因是它改变了原煤中的矿物组成。如要满足工业GE气化炉的运行要求,淮南煤和淮北煤均要配入比例高于50%的HM150煤。     

高温富氧燃烧过程中煤灰特征元素对煤粉成灰特性的影响

沾污结渣是富氧燃烧锅炉运行的主要问题之一,由于CO2和N2辐射传热和化学性质的差异,富氧锅炉内壁沾污结渣情况更加严重。近年来学者针对富氧情况下煤灰的沾污结渣情况进行了系统分析,得出了较为详实的结果,但仍缺乏富氧情况下基于煤灰内特征元素和气氛对于煤粉燃烧成灰的相关研究。选取煤粉结渣中的关键元素Ca、Na、Fe作为特征元素,选取特征元素的氧化物或氢氧化物作为添加剂,选取灰成分以Al、Si为主的山西无烟煤作为试验煤样,定量研究富氧情况下特征元素对于煤粉高温成灰特性的影响。结果表明,特征元素含量较高时,相比较空气气氛,富氧气氛下煤粉的反应时长减少20～50 min,且随氧气浓度增大,煤粉反应时长逐渐增加;高Fe煤和高Na煤的灰熔融温度比基准煤降低了150℃左右,但Ca对于煤灰的变形温度影响不明显;富氧情况下,高Ca煤中随着氧气浓度升高,出现钙硅铝酸盐和莫来石晶相,随温度升高,钙长石等硅铝酸盐生成,Na、Fe等元素非晶相化加强;高Fe煤中Fe随着氧气浓度升高从氧化物向硅铝酸铁转变,随温度升高,顽火辉石与磁铁矿含量升高,钙铁硅氧化物含量先增加后减少;高Na煤得到的低氧煤灰Na主要以霞石成分存在,氧气浓度升高导致其逐渐转化形成硅酸钠盐;随温度升高,Na的形态会从稳定的酸式盐向硅酸钠盐或其他稳定非晶体转变。     

Effects of Xinjiang high calcium coal co-firing on melting characteristics of Ca-bearing minerals in ash

In this study, a high-calcium coal, a high-silicon-aluminum Xinjiang coal and their blends were burnt in a drop tube furnace. The computer-controlled scanning electron microscope (CCSEM) was used to analyze the total ash mineral composition and particle size distribution after combustion. Based on CCSEM analysis, the composition data of single particle ash was obtained. The thermodynamic equilibrium method was used to calculate the liquid phase ratio of minerals in the ash, and the effect of coal blending on the melting characteristics of calcium-containing minerals in the ash was analyzed. The results show that the organically bound Ca easily interacts with other minerals in the coal. The mineral species of Ca-bearing minerals in the bulk ash mainly depend on the included minerals in coal. Co-firing will promote the conversion of calcium-containing aluminosilicate in the ash to calcium-containing complex aluminosilicate, and at the same time promote the melting of calcium-containing minerals. Under low temperature conditions, the particle size distribution of molten calcium-containing minerals in co-fired coal ash is affected by the particle size distribution of the alkali metal; however, under high temperature conditions, co-firing promotes the migration of molten calcium-containing minerals to large particle size ash.     

A mathematical model of ash formation during pulverized coal combustion

A mathematical model of ash formation during high-rank pulverized coal combustion is reported in this paper. The model is based on the computer-controlled scanning electron microscope (CCSEM) characterization of minerals in pulverized coals. From the viewpoint of the association with coal carbon matrix, individual mineral grains present in coal particles can be classified as included or excluded minerals. Included minerals refer to those discrete mineral grains that are intimately surrounded by the carbon matrix. Excluded minerals are those liberated minerals not or at least associated with coal carbon matter. Included minerals and excluded minerals are treated separately in the model. Included minerals are assumed to randomly disperse between individual coal particles based on coal and mineral particle size distributions. A mechanism of partial-coalescence of included minerals within single coal particles is related to char particulate structures formed during devolatilization. Fragmentation of excluded minerals, which is important particularly for a coal with a significant fraction of excluded minerals, is simulated using a stochastic approach of Poisson distribution. A narrow-sized sample of an Australian bituminous coal was combusted in a drop-tube furnace under operating conditions similar to that in boilers. The particle size distribution and chemical composition of experimental ash were compared to those predicted with the model. The comparisons indicated that the model generally reflected the combined effect of coalescence of included minerals and fragmentation of excluded minerals, the two important mechanisms governing ash formation for high-rank coals.     

Effects of coal blending on the reduction of PM10 during high-temperature combustion 2. A coalescence-fragmentation model

A coalescence-fragmentation model has been developed to predict the behaviors of coal mineral particles during the combustion of pulverized bituminous coals or coal blends. Based on the computer-controlled scanning electron microscope (CCSEM) characterization of coal minerals, the particle size distributions (PSDs) and mineral species of ash particles can be simulated. In particular, the interactions among excluded minerals (mainly referring to the excluded Ca-bearing-species and Fe-bearing-species) and included minerals are accounted for in this model. The PSDs and the mineral species of ash particles are derived from the coalescence and fragmentation of coal mineral particles. Based on this proposed model, both of the predicted PSDs and the mineral species of ash particles are in good agreement with their corresponding experimentally measured values. And the comparisons further demonstrate that the combined effects of coalescence of included minerals and fragmentation of excluded minerals have direct impacts on the ash-forming process. In addition, for the coals rich in excluded Ca- and/or Fe-bearing-species, the interactions among included minerals and excluded minerals are another important mechanism governing ash formation for high-rank coals.     

不同炉型潞安煤灰理化及酸/碱溶解特性

对潞安煤经循环流化床、煤粉炉和气化炉处理后得到的煤灰进行了化学组成、矿物组成、特征基团、粒径分布、比表面积及微观形貌等理化性质的对比研究,并考察了其在酸浸和碱浸过程中Al^3+,Si^4+,Fe^3+,Ca^2+,K^+和Ti^4+等离子的溶解特性。结果表明:不同炉型潞安煤灰中铝、钙、硫等元素的含量有明显的差异;矿物组成包括晶相的鳞石英、方石英、莫来石、硬石膏及非晶相的偏高岭石、假莫来石、无定型二氧化硅等;相比较而言,气化炉灰中铝硅酸盐矿物结构更加不稳定。循环流化床灰颗粒呈具有一定孔洞结构的不规则状,而煤粉炉灰和气化炉灰均为光滑球形颗粒,循环流化床灰的粒径>煤粉炉灰的粒径>气化炉灰的粒径,循环流化床灰的比表面积>气化炉灰的比表面积>煤粉炉灰的比表面积。在HCl溶液中,Al^3+,Fe^3+,Ca^2+,K^+,Ti^4+的溶出率均较高;在NaOH溶液中,仅Si^4+和K^+的溶出率较高。不同炉型潞安煤灰中各元素的溶出率具有较大差异,主要与其矿物组成、结构稳定性、粒径和比表面积等相关。     

The roles of lime and iron oxide on the formation of ash and deposits in PF combustion

This paper presents the results of a study to assess the slagging propensities of a suite of UK, Spanish and South African coals, ranging from lignites to anthracites. Laboratory deposits were collected on ceramic deposition probes at gas temperatures of ∼1250°C, using an entrained flow reactor that simulates the time-temperature conditions experienced by pulverised coal particles in a large utility boiler. The degree of sintering and consolidation of the deposits would not have been predicted from bulk ash chemistry, indicating the importance of mineral matter distributions in the pulverised coal. Deposits with similar base to acid ratios and Fe₂O₃ contents displayed a range of slagging propensities on CCSEM analysis, consistent with the visual ranking. CCSEM analysis of the fly ashes collected from the combustion gases revealed a similar chemical composition to the coal ash and ash collected at the base of the EFR. CaO was observed to have readily assimilated into the aluminosilicate fly ash particles. On deposition, the CaO distribution largely remained unchanged. Fe₂O₃ was redistributed on forming a deposit possibly aided by CaO already dissolved in the aluminosilicates. The study provides an insight into the observations made by boiler operators burning coals with high CaO and Fe₂O₃ ashes.     

Ash Vaporization in Circulating Fluidized Bed Coal Combustion

ABSTRACT

In this work, the vaporization of the ash forming constituents in circulating fluidized bed combustion (CFBC) in a full-scale 80 MW_th unit was studied. Ash vaporization in CFBC was studied by measuring the fly ash aerosols in a full-scale boiler upstream of the electrostatic precipitator (ESP) at the flue gas temperature of 125°C. The fuel was a Venezuelan bituminous coal, and a limestone sorbent was used during the measurements. The fly ash number size distributions showed two distinct modes in the submicrometer size range, at particle diameters 0.02 and 0.3 μm. The concentration of the ultrafine 0.02-μm mode showed a large variation with time and it decreased as the measurements advanced. The concentration of the 0.02-μm mode was two orders of magnitude lower than in the submicrometer mode observed earlier in the bubbling FBC and up to three orders of magnitude lower than in the pulverized coal combustion. Scanning electron micrographs showed few ultrafine particles. The intermediate mode at 0.3 μm consisted of particles irregular in shape, and hence in this mode the particles had not been formed via a gas to particle route. We propose that the 0.3-μm mode had been formed from the partial melting of the very fine mineral particles in the coal. The mass size distribution in the size range 0.01–70 μm was unimodal with maximum at 20 μm. Less than 1% of the fly ash particles was found in the submicrometer size range. Ninety percent of Mg in coal was organically bound, and it was found to react with quartz and aluminosilicate minerals inside the coal particle. No Mg was found to be released to the gas phase and Mg mass fraction size distribution was size independent. A fraction of halogens CI, Br and I were found to be in the gas phase after the combustion.     

水煤浆气化炉内飞灰的形成机理

基于实验室规模的多喷嘴对置式水煤浆气化炉,利用SEM、马尔文激光粒度仪和XRD表征气化炉内飞灰的粒径分布和组成,并分析了气化炉内飞灰的形成机理。结果表明,喷嘴平面处飞灰与气化炉出口处飞灰的粒径分布及化学组成存在显著差异,不同气化阶段飞灰的形成机理也不同。气化燃烧阶段飞灰的形成机理为部分固定碳燃烧和外在矿物转化,而在焦炭气化反应阶段,飞灰的形成机理为焦炭破碎和内在矿物释放及转化。     

Coal and coal ash characteristics to understand mineral transformations and slag formation

A knowledge of the composition and structure of minerals in coal is necessary in order to understand the mineral transformations and agglomerate or slag formation during combustion or gasification. Coal ash fusibility characteristics are difficult to determine precisely, partly because the ash contains many components with different chemical behaviours, and may vary from coal source to coal source.The first objective of this study was to determine if the most relevant characteristics of coal were representative of the typical coal from the South African Highveld region. Secondly, a detailed understanding of the coal and coal ash are needed in order to explain slag formation and mineral transformations.Based on standard coal properties, such as the ash content, volatile content, carbon content and maceral composition, it can be concluded that the coal sample used for this study was representative and comparable with the coal from the Highveld region.From the results obtained and the analysis done on the coal samples, it was observed that the mineral grains showed a wide range of types that ranged from pure coal to pure minerals. The types of mineral particles within the coal range from large irregular minerals to small irregular minerals on the edge of coal particles. Kaolinite and quartz can occur as fine inclusions in carbon rich particles or associated with mudstone, siltstone or sandstone, together with kaolinite infillings. The main minerals present in the coal feed are kaolinite, quartz, dolomite, calcite, muscovite, pyrite and microline. An abundance of calcium-rich particles, which are probably calcite and dolomite, were observed. These minerals are present throughout the coal structure and are not specific to one type of mineral grain or structure. An increase in Si and Al abundance in three different prepared coal fractions with increasing particle size distribution was observed the high density fractions are mainly situated in the coarser particles.After combustion or gasification, the major source of glass is derived from included minerals in carbon rich particles. It is clear that focus on the modification of the unclassified/amorphous phase, to increase viscosity (decrease slag formation or have a higher concentration of crystalline phases) at a certain temperature, or in general terms the ash fusion temperature of the coal, is important. Altering the ash chemistry involves the addition of a material to the coal to increase the viscosity.