准东煤燃烧中矿物质转化行为的CCSEM研究

在沉降炉中进行了准东煤的燃烧实验,利用计算机控制扫描电镜技术(computer controlled scanning electron microscopy,CCSEM)研究了煤中矿物质的转化行为。研究表明煤中主要矿物为方解石、高岭石、含铁类物质以及未分类矿物,燃烧后灰中石英、铁的氧化物、白云石的含量急剧增加,未分类矿物和方解石的含量下降。同时对3种重要致渣元素Na、Fe、Ca在燃烧前后的矿物转化行为及颗粒粒径分布进行了详细研究。     

神东地区侏罗纪煤中矿物的热转化特性

利用光学显微镜和X射线衍射(XRD)对神东侏罗纪煤中矿物富集样品进行分析,考察神东煤中的主要矿物种类,采用XRD和热重分析研究了气化条件下随温度变化神东侏罗纪煤中矿物的热转化特性,结合热力学软件FaceSage对煤中矿物热转化特性进行模拟。结果表明:神东侏罗纪煤中的矿物主要有黏土矿物、碳酸盐矿物(方解石)、硫化铁类矿物(黄铁矿)、刚玉、石英和赤铁矿;煤灰受热过程中主要发生碳酸盐矿物和硫酸盐类矿物的分解反应及钙铝黄长石、硅灰石和钙长石的形成反应等,在整个煤灰熔融过程中,硅铝酸盐类矿物起着骨架支撑的作用;FactSage能够较准确地模拟煤灰熔融过程发生的矿物热转化行为,神东煤灰受热过程中液相是在900℃左右开始形成,完全转变为液相的温度是1 286℃。     

钙及其赋存形态对煤热解过程中氮转化的影响

燃煤NO_x生成与煤中含氮物质的种类及其在热解、燃烧中的转化特性密切相关。利用酸洗—物理混合/溶液浸渍添加方法制备获得含不同赋存形态Ca的煤粉,在水平管式炉上研究了不同赋存形态Ca对煤热解过程中氮转化特性的影响。结果表明,无机形式存在的Ca会使热解后的焦氮含量升高,而有机形式存在的Ca倾向于降低热解后的焦氮含量。添加以Ca(OH)2为模型物质的无机含钙矿物会抑制煤热解过程中NH_3的生成。添加以醋酸钙为模型物质的外在或内在有机含钙矿物后,NH_3均降低而HCN生成量升高,表明有机含钙矿物会促进煤中氮向HCN的转化。与以外在矿物形式添加的醋酸钙相比,以内在矿物形式添加的醋酸钙对热解中氮转化行为的影响较小。     

煤中矿物万分对粉煤灰性质的影响

本文对煤及其粉煤灰的矿物成分进行了系统分析，阐述了煤中矿物成分在电厂锅炉燃烧过程中的转化过程，总结了煤中矿物成分对粉煤灰矿物成分及粉煤各种性质的影响。     

煤焦化过程中矿相转变规律

利用XRD和物相定量分析方法研究了南桐和永混煤及含添加剂的南桐煤在焦化过程中的矿相转变规律. 结果表明,南桐煤焦化过程中,占灰分含量46.03%的高岭土完全分解,其中65.24%分解生成莫来石,17.02%分解生成方石英和γ氧化铝. 灰分中石英类矿物含量由19.57%升至35.48%,含量为7.83%的黄铁矿中89.53%转化为磁黄铁矿,含量为17.64%的方解石完全分解且部分生成CaH2PO4. 永混煤焦化过程中,除方解石主要转化为褐硫钙石和硬石膏之外,其他矿物质的转变规律与南桐煤相近. 在南桐煤中添加5% CaO和Fe2O3焦化后,主要产物莫来石相较于添加前分别下降4.80%和5.68%,石英类矿物下降21.17%和20.17%. 同时,添加剂提高了焦炭中含钙和含铁催化性矿物的含量,且焦炭的反应性分别提高31.45%与15.05%.     

煤中含铁矿物在煤粉燃烧过程中行为的研究进展

综述了国内外关于煤中煤中含铁矿物在煤粉燃烧过程中行为及其在结渣过程中作用的研究进展,着重对硫铁矿（ＦｅＳ２）菱铁矿和伊利石在燃烧过程中行为的研究结果进行了评述,并指出了这方面值得进一步研究的内容。     

红外光谱分析淮南煤灰中矿物组成

选取淮南矿区HN115与HN119两种煤样,在氧化性气氛下,制成815℃煤灰。利用红外光谱研究了其矿物质组成以及煤中添加不同比例助熔剂CA后矿物组成的变化。结果表明:淮南煤灰中,矿物质组成为石英、硬石膏、方解石、高岭土和赤铁矿,其中硬石膏和方解石含量较低。煤中添加助熔剂CA后,煤灰中硬石膏含量增加,并且随着助熔剂CA量的不断增加,方解石含量在不断减少,硬石膏含量在不断增加。     

热重法研究逐级脱矿对褐煤燃烧特性的影响

以胜利褐煤和昭通褐煤为研究对象,采用H_2O、HCl/CH_3COONH_4及CH_3COONH_4/HCl/HF对褐煤进行逐级脱矿处理,利用XRF、XRD和SEM对褐煤中的矿物质种类、含量及其形貌进行分析,采用热重法对比分析了脱矿前后煤样的燃烧特性及动力学反应过程,分析了矿物质对褐煤燃烧特性的影响。结果表明:两种褐煤中的主要矿物元素为Si、Al、Fe、S及碱/碱土金属元素,主要矿物组成为石英、高岭石、云母、石膏、方解石和黄铁矿;3种脱矿方式的矿物质脱除率分别为:胜利褐煤1.22%、32.49%、97.90%,昭通褐煤0.47%、26.41%、94.79%;原煤及脱矿煤的综合燃烧指数S的大小顺序为:原煤HCl/CH_3COONH_4脱矿煤H_2O脱矿煤CH_3COONH_4/HCl/HF脱矿煤,胜利及昭通褐煤呈现相同的规律。三级脱矿处理显著改善了煤的综合燃烧性能。煤中以羧酸盐形式、配位键形式存在于含氧或含氮官能团上的碱及碱土金属对煤的燃烧存在促进作用。煤中水溶性矿物质对燃烧具有抑制作用。褐煤燃烧从着火温度到燃尽温度这一温度区间满足一级反应方程,且线性相关性系数R均在0.985以上。     

煤中典型矿物在高温下演变规律

煤中典型矿物可以分为6种:黏土矿物、硫化物、磷酸盐、碳酸盐、硫酸盐和其他矿物。煤中矿物在升温过程中的演变过程对煤灰黏温特性影响较大,因此煤中矿物构成对煤炭的应用范围和利用途径造成一定的影响。通过研究煤中主要矿物的构成和不同矿物组合在升温过程中的变化规律,可为气化原料煤的选择和调节气化用煤煤灰黏温特性提供参考。笔者阐述了煤中主要矿物在高温下的转化过程及其主要产物。将高岭石、伊利石、黄铁矿等8种矿物根据矿物特性分为3组,采用FactSage软件在1 000～1 600℃进行了模拟研究。计算过程中选择惰性气氛,每隔100℃进行一次计算,每个矿物均以1 mol的量参与计算,出现新的矿物或旧矿物消失的条件下,该温度点的矿物组成也进行模拟计算。研究结果表明,高岭石和伊利石组成的系统在1 600℃时仍存在莫来石,透长石在1 145℃消失,1 145～1 286℃生成了白榴石。黄铁矿、磷灰石、方解石、菱铁矿、石膏、石英组成系统生成的铁尖晶石在1 106℃消失,羟基磷灰石在1 455℃时消失。当8种矿物共存时,生成的羟基磷灰石在1 285℃时消失,莫来石在1 118℃时消失。1 448℃后固体大部分进入熔渣。莫来石是煤中典型的耐高温矿物,当煤灰中低熔点矿物形成熔渣后,可与莫来石反应生成低温共熔物,降低了煤灰中固体物质的含量,有利于改善煤灰黏温特性。     

五彩湾煤中钠在燃烧过程中的迁移释放规律

采用不同萃取液对新疆准东高钠煤进行逐级萃取实验, 分析了煤中钠的存在形式。分别检测了不同温度下五彩湾煤原煤以及815℃下不同萃取方式处理的煤燃烧后煤灰中钠的含量, 研究了五彩湾煤燃烧过程中钠的迁移释放规律。并且对传统灰分分析方法和微波消解-电感耦合等离子体原子发射光谱仪分析法(微波消解-ICP-AES分析法)测量煤中钠含量进行了比较。实验结果表明, 新疆高钠煤中钠主要为水溶钠。五彩湾煤燃烧过程中, 钠的释放主要发生在815℃之前, 并且以水溶钠和有机钠的释放为主。不同存在形式的钠在燃烧中存在转化, 主要表现为水溶钠向不可溶钠的转化以及不可溶钠向有机钠的转化。通过比较, 微波消解-ICP-AES分析法对煤中钠含量的分析更准确。     

提高新疆准东露天煤成浆性的实验研究

为提高准东露天煤的成浆性能,利用宽沟煤、乌东煤、北山煤、黑山煤、红沙泉煤5种煤与准东露天煤进行了混合制浆实验,考察了各单种煤的成浆性能以及单种煤最高成浆浓度条件下混合制浆的煤浆性能。单一准东露天煤浆的成浆性研究表明:准东露天煤单独制浆时,在添加剂添加率3‰下,煤浆最高质量分数为47%,黏度650 mPa·s,但煤浆流动性和稳定性一般。与不同种煤混合制浆研究表明:准东露天煤与宽沟煤、黑山煤容易混合成浆,煤浆的浓度、流动性、稳定性均有明显提高;在准东露天煤与宽沟煤、黑山煤质量比5∶5时,煤浆质量分数可达57%,可满足水煤浆气化炉生产对煤浆的要求。     

An investigation on the heterogeneous nature of mineral matters in Assam (India) coal by CCSEM technique

This is a very first preliminary investigation on the distribution of heterogeneous nature of mineral matter in one of the industrially important Assam (India) pulverized coal using computer-controlled scanning electron microscopy (CCSEM). The results show that clay minerals, quartz, pyrite, and pyrrhotite form the bulk of the mineral matter. Minor minerals, such as calcite, dolomite, ankerite, barite, oxidized pyrrhotite, and gypsum, are also observed in the sample. The particle size distribution (PSD) of the included minerals is generally observed to be finer than that of the excluded ones in the coal. As a consequence, the coal rich in included minerals has more small mineral particles, which may affect its reactivity. Regarding the association of individual mineral species, the proportion of included to excluded is found to be higher in major cases. With regard to the modes of occurrence of major inorganic elements, it is found that Si mostly occurs as quartz and clay minerals, while Al mostly occurs as silicate minerals. Fe is primarily present as iron sulfides, iron oxide, and Fe-Al-silicate. S is partitioned into iron sulfides and gypsum. Most Ca occurs as carbonates and gypsum, with a minor fraction associated with clay minerals. Mg is mainly present as dolomite and clay minerals, with a very minor fraction present as ankerite. The majority of alkali elements are associated with aluminosilicates. P is mostly associated with kaolinite and/or present as more complex compounds containing Al, Si, and other elements as apatite is found to be absent in the coal studied. Ti is mainly present as rutile and kaolinite.     

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。     

合成煤中钠对煤燃烧及灰特性影响

准东煤中钠含量高，燃用时锅炉会出现严重结渣问题。通过向准东煤为原料制取的超纯煤中添加灰的模型化合物，得到合成煤。并在此基础上利用热重-差示扫描量热分析法（TG/DTG/DSC）、X射线衍射仪（XRD）和灰熔融温度测定分析手段，研究Na₂O含量对煤燃烧特性和灰熔融性的影响。结果表明：钠主要影响合成煤的着火温度（T_i）与焦炭燃烧阶段，钠含量增加使T_i升高，并且Na₂O在灰中质量分数由5%升高至8%后，钠含量增加使焦炭燃烧速率先减小后加快，并能够改善煤粉燃尽特性。钠能够降低灰熔融温度，并在Na₂O质量分数高于5%后，温度下降更加明显。在三元相图中钠对莫来石的助熔作用是造成灰熔融温度降低的重要原因。XRD分析表明Na₂O含量增加，充当骨架作用的石英在钠的助熔作用下与难熔矿物硅钙石、MgO等生成低熔点长石类矿物，这类矿物在高温下有助熔作用，能够降低灰熔融温度。同时还生成助熔性含钠矿物霞石，加剧了灰熔融。     

锅炉全烧准东煤沾污结渣特性分析

针对燃烧新疆准东煤存在结渣、沾污等问题,在新疆宜化150 t/h锅炉全烧准东煤进行实炉测试试验。在全烧准东煤期间,对锅炉炉膛水冷壁、过热器、低温受热面、底渣的结渣形态观测,对以上各部位渣样取样分析。结果显示,锅炉全部燃烧准东煤时存在严重的结渣与沾污问题。结合实验室试验研究及本次实炉测试试验,认为结渣、沾污主要原因是由于煤中钠的氯化物、氧化物、单质气化后形式挥发到烟气中冷凝在高温管壁,与烟气SO_2、Fe_2O_3等化合生成硫酸盐沉积,煤中铁矿石分解后与CaO、Al_2O_3等形成低温共融化合物,降低灰熔融性温度,增加准东煤灰结渣、沉积倾向,煤中高钙、高水分加速了烟气低温段的积灰。     

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.     

煤矸石灰添加对准东煤灰熔融特性影响

选取两种准东煤（ZDA和ZDB）为研究对象，利用灰熔融温度测定仪、X射线荧光光谱和X射线衍射仪考察了单一准东煤灰及其与煤矸石（CG）灰掺混后酸碱比、化学组成和矿物质演变对灰熔融特征温度的影响规律。结果表明高温下ZDA中主要矿物组分为霓辉石和赤铁矿等助熔矿物，而ZDB中以难熔矿物硫铝酸钙与镁硅钙石为主，导致ZDA灰熔融温度明显低于ZDB。随着CG灰质量分数增加，ZDA/CG与ZDB/CG熔融特征温度呈现先下降后上升趋势，分别在CG灰添加比40%和60%时出现最小值；当ZDA/CG与ZDB/CG酸碱比接近时，CaO与Fe₂O₃含量是影响变形温度与流动温度的主要原因。对于上述两种高碱性煤灰，含钙矿物对于灰熔融特性影响较大，而含钠矿物的影响相对较小。本文旨在为改善准东煤灰沉积倾向提供基础数据。     

CO2气氛下准东煤化学链燃烧特性研究

我国准东煤储量丰富,钠含量高。以高钠准东煤为燃料,CO₂为气化介质,铁矿石为载氧体,基于鼓泡流化床反应器开展准东煤化学链燃烧特性的实验研究,考察了煤粒径、温度、流化风速和煤焦粒径对煤及煤焦化学链燃烧过程中可燃气体逃逸规律的影响;同时研究了煤中矿物质对煤焦气化过程的影响。结果表明,在基于鼓泡流化床实施的煤化学链燃烧过程中,由于煤颗粒和载氧体床料流化特性差异大,存在离析现象;离析影响煤化学链燃烧过程中挥发分和焦炭的转化;较高流化风速可显著增强载氧体与煤/焦炭颗粒的混合,有效改善离析对可燃气体转化的影响,降低可燃气体逃逸,并加快焦炭气化速率;煤焦中的矿物质能够维持煤焦较快的气化速率。     

Low cost catalytic sorbents for NOx reduction. 1. Preparation and characterization of coal char impregnated with model vanadium components and petroleum coke ash

Spanish coal, char and activated char doped with model vanadium components (V₂O₅ and NH₄VO₃) and petroleum coke ash (enriched in V, Fe, and Ni) were prepared and characterized as potential catalytic sorbents for NO_x reduction. The phase-mineral and chemical composition, content and behavior (capture, retention, distribution, and redistribution) of transition metals, as well as morphogenesis, surface area, acid-base properties, surface active sites and oxidation-reduction transformations of the catalytic sorbents were characterized. It was found that minerals and phases such as anhydrite, calcite, clay minerals, pyrite, pyrrhotite, magnetite and fusinoid-type ingredients have a leading role for the behavior of loaded transition metals. Some original (pyrite, jarosite, shcherbinaite, coulsonite, trevorite, Ni oxide) and newly formed (pyrrhotite, magnetite, wuestite, hematite, paramontroseite, karelianite) Fe, V and Ni minerals in the catalytic sorbents are perspective redox indicators for the physicochemical conditions in such complex system. The data indicate that the V-Fe-Ni containing minerals dispersed onto and into the carbon support may be the most active catalytic sites. The preparation procedure that could provide the most favorable conditions for the production of effective and low cost catalytic sorbents for NO_x reduction is also described.