Nature of insoluble residues accumulated during hydrogenation of Victorian brown coals

The carbonaceous material and mineral matter in hydrogenation residues from two Victorian brown coals have been characterized. Preliminary data indicate that the mineral and inorganic content of the coal may be related to the formation of different types of carbonaceous solids. The minerals such as quartz, kaolinite and halite appear to be essentially unchanged by hydrogenation, whereas pyrite is reduced to pyrrhotite. Some iron carboxylate also reacts under hydrogenation conditions to form pyrrhotite. The type of carbonate species formed during hydrogenation depends on the distribution of exchangeable cations present in the coal and when high levels of Mg are present in addition to Ca, dolomite is the predominant carbonate phase.     

Occurrence,abundance and origin of minerals in coals and coal ashes

The mineralogy of coal and coal ash samples from a wide variety of deposits worldwide has been studied by X-ray diffractometry, light microscopy, SEM, TEM, and DTA-TGA methods. The common major minerals identified in the crystalline matter of coals are quartz, kaolinite, illite, calcite, pyrite, plagioclase, K-feldspar and gypsum, and occasionally dolomite, ankerite, siderite, Fe oxyhydroxides and sulphates. A number of minor and especially accessory minerals are also present. The modes of occurrence and some genetic peculiarities of the minerals found are described and summarized. Minerals and phases of probable detrital origin include mainly silicates, volcanic glass, oxyhydroxides and phosphates. Authigenic minerals of syngenetic origin may be sulphides, clay minerals, carbonates and rarely sulphates and phosphates. Epigenetic minerals, formed by the infiltration of low-temperature hydrothermal solutions, may include sulphides, carbonates, sulphates, clay minerals, quartz, chlorides, and probably alkaline-earth hydroxides and zeolites. The alteration products of detrital and authigenic minerals may be Fe and Al oxyhydroxides, sulphates, kaolinite, illite, chlorite, muscovite, zeolites and calcite. The behaviour of these minerals and phases during low- and high-temperature ashing is also discussed.     

Partitioning of minerals and elements during preparation of Taixi coal, China

Mineralogy, sulfur and 40 other element contents were determined on eight samples of the Taixi coal and its preparation products from the Rujigou mining district, China. INAA, ICP-AES, CV-AAS, GAAS, XRD, SEM/EDX, conventional chemical and maceral analysis were carried out on the samples. This study is focused on the partitioning behavior of the minerals and elements during the coal cleaning, and the main factors influencing the partitioning behavior of elements were also discussed.The clay minerals (kaolinite, illite, montmorillonite and chlorite), quartz and, to a lesser extent, carbonate minerals (calcite, dolomite and siderite) dominate the mineralogy of Taixi coal. There is also minor amounts of pyrite and trace amounts of gypsum and feldspar. The quartz is dominantly epigenetic in origin, and clay minerals were modified by the thermal metamorphism. They are easily liberated from the coal by cleaning. However, although the majority of carbonate minerals are also mainly epigenetic in origin, its degree of removal is relatively low, especially with respect to dolomite and siderite, which are often finely dispersed in coal macerals, so that they are mostly retained in cleaned coal. Most of the elements studied could be removed effectively during the cleaning processes, especially for the elements predominantly hosted in coarse, epigenetic minerals. Compared with other sized cleaned coals, the coarse-grained cleaned coal is cleanest and has a relatively low potential of environmental risk. The majority of the potentially hazardous elements are notably enriched in the coal waste so that the waste is not feasible to be used as fuel. The partitioning of elements during the coal cleaning processes is essentially controlled by some factors such as the modes of occurrence of elements, maceral type, grain size and textural relation of minerals, and types of cleaning technique used.     

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。     

皖北刘二煤在Shell气流床气化过程中熔渣形成机理初探

选取安庆石化sheu气化炉使用的皖北刘二煤（简称AQ007）及气化过程产生的大块渣和细渣样品，利用X-射线衍射仪（XRD），考查了AQ007煤在弱还原性气氛下不同加热温度下煤灰熔融过程中的矿物演变过程，对煤灰的熔融机理进行了探讨，对Shell气化过程产生的大块渣和细渣的晶体矿物组成进行了对比研究。结果表明：AQ007煤中的主要晶体矿物有高岭石、石英、方解石、白云母等。在还原性气氛下，煤灰随着温度的升高，石英、硬石膏等结晶矿物含量逐渐减少，生成新的矿物质，莫来石的生成是导致AQ007煤灰熔点高的主要原因。大量钙长石的生成是导致安庆石化sheu气化炉产生大块熔渣和堵渣主要原因。     

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.     

贵州六盘水煤矸石的矿物特性

对贵州六盘水地区煤矸石的矿物特性进行了研究. 结果表明,以煤巷矸和岩巷矸混合矸为主的煤矸石固定碳含量和热值均较低,不适宜直接用于动力燃料发电,而富铝、高铁、高钙是其重要特征,SiO2, Al2O3和Fe2O3含量之和达70%~80%,所含V, Co, Ni, Cr, Ge的富集度高,均具有回收利用价值. 矿物组成以石英和高岭石为主,其次为菱铁矿、黄铁矿、蒙脱石、斜长石、伊利石、白云石、方解石、锐钛矿等;粉末状煤矸石由大小不一的不规则颗粒组成,粒径多为1~3 mm,部分粒径为0.2~1 mm;石英、菱铁矿、黄铁矿等晶体矿物多呈致密块状,结晶完整;高岭石、蒙脱石、伊利石等多呈片状、疏松团块状,结晶较石英差;而含碳有机质多呈片状,呈无定型.     

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%.     

Identification of clay minerals in coal and wastes from main coal washery, Zonguldak, Turkey

Identification of clay minerals present in coal and washery wastes is important in cleaning fine coal by froth flotation and in flocculation and dewatering. Therefore samples of wastes from jigs and the flotation cell at the Zonguldak main coal washery were collected and analyzed petrographically for their mineral matter content and by X-ray diffraction for their clay content. The “loss on ignition” method was carried out to determine their organic carbon and carbonates. The waste samples contain 48–68% clay minerals in addition to silicates, carbonates, sulfides and coal. Three clay minerals were identified, namely illite, kaolinite and chlorite. Illite seemed to be the dominant clay mineral in washery wastes. Loss on ignition indicated high percentages of organic matter in the fine jig tailings (21%) and flotation tailings (33%). 3%–6.5% of carbonates have also been found.     

Studies on slag deposit formation in pulverized-coal combustors. 4. Comparison of sticking behaviour of minerals and low-temperature and ASTM high-temperature coal ash on medium carbon steel substrates

Sticking test results indicate that high-temperature melts containing iron sulphide (pyrrhotite) spread well over an oxidized mild steel surface and the adhesion forces are comparatively high even at low metal temperatures. This sulphide phase originates in the coal as pyrite. Alkalis substituted in the clay structure of both illite and montmorillonite led to the formation of lower-melting slag drops compared to kaolinite. Potassium and chlorine present in the slag drops, formed from the low-temperature ash (LTA) of a Wilcox belt Texas lignite, also led to enhanced sticking properties. The sticking behaviour of slag drops formed by the rapid melting of coal minerals, either LTA residue or synthetic mineral combinations, differed from that of the ASTM ash or synthetic metal oxide mixtures. Any tests, including the sticking test using the bulk minerals or ash composition of a specific coal, may not correlate with slag deposit formation in a utility boiler, as indicated by non-agreement between the test results with the Upper Freeport ash residues and operating experience at Keystone Generating Station.     

Behaviour of coal mineral matter in sintering and slagging of ash during the gasification process

The mineral matter in typical feed coals used in South African gasification processes and the ash derived from gasifying such coals have been investigated using a variety of mineralogical, chemical and electron microscope techniques. The mineral matter in the feed coals consists mainly of kaolinite, with minor proportions of quartz, illite, dolomite, calcite and pyrite plus traces of rutile and phosphate minerals. The calcite and dolomite occur in veins within the vitrinite macerals, and are concentrated in the floats fraction after density separation. Some Ca and Ti also appear to be present as inorganic elements associated with the organic matter.Electron microscope studies show that the gasification ash is typically made up of partly altered fragments of non-coal rock, bonded together by a slag-like material containing anorthite and mullite crystals and iron oxide particles, with interstitial vesicular glass of calcic to iron-rich composition. Ash formation and characteristics thus appear to be controlled by reactions at the particle scale, allowing the different types of particles within the feed coal to interact with each other in a manner controlled mainly by the modes of mineral occurrence. Integration of such techniques provides an improved basis for evaluating ash-forming processes, based on quantitative phase identification, bulk and particle chemistry, and the geometric forms in which the different phases occur.     

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.     

Reduction of iron sulphates during coal liquefaction

The transformation of pyrite to pyrrhotite and gypsum to anhydrite is well known during coal liquefaction. Most coals, except extremely fresh ones, contain various iron sulphates resulting from the oxidation of pyrite and marcasite. The reduction of iron sulphates to pyrrhotite during liquefaction is shown with the degree of reduction being temperature dependent. The formation of pyrrhotite from the iron sulphates is important because pyrrhotite is considered to catalyse hydrogénation reactions.     

脱矿物质过程对煤结构影响的研究

选取神华煤和兖州煤两种煤样,用盐酸和氢氟酸处理脱去其中的矿物质,并且脱矿物质前后的煤样在氧化性气氛下,制成815℃的煤灰。利用红外光谱研究其矿物质组成以及处理前后煤结构的变化。结果表明：酸处理法能够脱除煤中大多数矿物质。2种煤灰中,矿物质组成主要是石英、硬石膏、方解石、高岭土和含铁矿物质,但含量不同。处理前后,煤结构中的含氧官能团发生了一定的变化。     

Mineralogy of ash of some American coals: variations with temperature and source

Ten samples of mineral-matter residue were obtained by the radio-frequency low-temperature ashing of subbituminous and bituminous coals. The low-temperature ash samples were then heated progressively from 400 °C to 1400 °C at 100 °C intervals. Mineral phases present at each temperature interval were determined by X-ray diffraction analyses. The minerals originally present in the coals (quartz, kaolinite, illite, pyrite, calcite, gypsum, dolomite, and sphalerite) were all altered to higher temperature phases. Several of these phases, including kaolinite, metakaolinite, mullite, anhydrite, and anorthite, were found only in limited temperature ranges. Therefore the temperature of formation of the ashes in which they occur may be determined. Mineralogical differences were observed between coal samples from the Rocky Mountain Province, the Illinois Basin, and the Appalachians; and as a result of these mineralogical differences, different high-temperature phases resulted as the samples were heated. However, regional generalizations cannot be made until a greater number of samples have been studied.     

Distribution of inorganic and organic substances in the hydrocyclone separated Slovak sub-bituminous coal

A low-rank Slovak sub-bituminous coal from the Handlová deposit was physically treated by washing in a water-only cyclone with the goal to find the separation effect for inorganic (mainly Fe-bearing minerals) and organic substances (humic acids, diterpanes). A high-quality coal product with the ash content in the dry matter of 9.02% and carbon content of C^d = 68.12% at a mass yield of 29.51% was obtained using the water-only cyclone processing. At first, the physically treated coal samples were detailed characterized by XRD, ⁵⁷Fe Mössbauer spectroscopy, FT-IR and HR-TEM. In addition to non-crystalline organic coal components, inorganic compounds belonging to silicate minerals (kaolinite, muscovite and quartz) as well as to Fe-bearing sulphide minerals (pyrite) were identified in the sub-bituminous coal by XRD. ⁵⁷Fe Mössbauer spectroscopy detected the presence of iron carbonate (siderite), iron-containing clay mineral and two sulphur-containing minerals (pyrite, jarosite) in the untreated coal. On the other hand, only one Fe-bearing mineral, (pyrite) was found in the washed coal. Effect of the physical separation is also demonstrated in FT-IR spectra, where the peak at 1040 cm⁻¹ representing the silicate component in the untreated sample is not detectable in the washed coal sample. Presence of extractive organic substances, i.e. humic acids and tetracyclic diterpane (16α(H)-phyllocladane), in the hydrocyclone products is also evidenced. It was confirmed that the isolated diterpenoic compound is attendant in the washed product with the lowest ash content and it is assimilated with the organic part of coal. Surprisingly, humic acids were found in the highest concentration in the slurry that has the highest content of ash (63.14%).     

Use of differential scanning calorimetry in measuring the thermal decomposition of mineral carbonates occurring in coal

Differential scanning calorimetry (d.s.c.) was used to measure in nitrogen the enthalpies of decomposition of mineral carbonates occurring in coal, namely magnesite, siderite, calcite, dolomite and ankerite. Measured values were compared with calculated values, and reasonable agreement was obtained provided that heat losses from the sample were minimized. In air, magnesite, dolomite, ankerite and calcite afforded large negative contributions to the calorific value of coals, whereas siderite produced a small positive calorific contribution.     

Mineralogical and industrial characterization of the Batn El-Ghoul clay deposits, southern Jordan

The non-calcareous and thinly laminated Batn El-Ghoul clay deposit is a part of the Clayey Shale Unit of Lower Silurian age in Jordan. Its thickness is of about 50 m and it overlies a bituminous clayey deposit. 128 samples were selected from three boreholes and afterwards were subjected to detailed petrological, mineralogical and chemical analyses. The clay deposit is essentially composed of kaolinite as predominant mineral, with subsidiary mica-illite, vermiculite, smectite, chlorite, and mixed-layer mica-smectite. The non-clay minerals are quartz, feldspars, goethite and, occasionally, secondary gypsum. The Fe₂O₃ content is relatively high (7%) and is a detrital mineral. Palynomorph assemblages suggested a marine environment although authigenic micas are common. The clay deposits originated from highly weathered surfaces related to the basement. Industrial tests have proved the suitability of the clay deposit for ceramic industry.     

河南淅川木变石宝石学研究（下）

以中国河南淅川木变石为对象,利用现代测试技术对其宝石学特征进行研究。首先对其进行常规测试,矿片镜下分析得出样品里面主要的矿物成分是石英和钠闪石;通过X射线粉末衍射得出灰蓝色样品的主要成分是石英、方解石、白云石和重晶石,黄色样品的主要成分是石英、钠闪石和铁白云石;拉曼光谱测试结果显示灰蓝色样品因为其具有显著的466cm-1特征拉曼峰所以可以判断其属于二氧化硅类,褐黄色样品的拉曼谱峰,因为其具有显著的467cm-1特征拉曼峰所以可以判断其属于二氧化硅类即石英[4],其中1089cm-1代表了闪石类矿物的Si-O伸缩振动,所以黄色基底部分主要的物质应是二氧化硅,此外还有闪石类矿物红外吸收光谱显示样品具有相同的反射谱峰1158cm-1、816cm-1、704cm-1、565cm-1和520cm-1,结果显示这些谱峰均属石英,表明样品主要是由石英组成;通过激光诱导离解光谱分析出样品的主要元素是Si、Na、Mg、Ca等,次要元素是Be、Cu、Ag、Pd、Ca、Al、Pb等,而致色元素则是Fe。     

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。