Glow discharge excited low temperature ashing: A new technique for separating mineral matter of coals

Low temperature ashing techniques are widely used to determine mineral matter content and in the analysis of the composition of the inorganic matter in coal and coal products. This Paper presents a new technique which makes it possible to ash coals in 4 (low-rank coals) to ≈8 (high-rank coals) h per gramme. The problem of the formation of LTA artefacts is described and differences between authigenic and artefactic minerals are indicated.     

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.     

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.     

The inorganic geochemistry of coal,petroleum, and their gasification/combustion products

The inorganic makeup of coal and petroleum differ in several crucial ways. The origins of these differences include the disparate geologic environments of formation, the contrasting parent materials (plant versus planktonic) and hence distinct organic species, and the physical state of the fuels (solid versus liquid). The inorganic chemistry of petroleum is usually controlled by the type and abundance of its organic compounds (i.e., V, Ni, ± Fe-bearing porphyrins and S-bearing thiols, sulfides, disulfides, thiophenic derivatives, resins, and asphaltenes), with significant, though often smaller contributions from entrained mineral phases. This near balance of inorganic compositional control causes petroleum to form combustion/gasification (pyrochemical) slag and ash with a large number of elements (i.e., V, Ni, S, Fe, Ca, Na, K, Mg, Si, and Al) in significant relative concentrations. This balance provides also opportunities for large departures from any given “norm”. The inorganic chemistry of coal, on the other hand, is dominantly controlled by its contained detrital and authigenic mineral matter, with relatively small contributions from organically carried elements other than sulfur. Detrital minerals are those that survive the geological processes of weathering and transport, and hence are a small group of physically resistant and chemically stable minerals including quartz, clay minerals, and oxides of Fe and Ti. The most abundant authigenic minerals in coal include clay minerals, pyrite/marcasite, carbonates, Ca- and Fe-sulfates, and Fe-oxides and hydroxides. Pyrochemical slag and ash from coal are therefore primarily enriched in Si, Al, Ca, Fe, and S. From a processing standpoint, the behavior of slag and fly ash is largely a function of the complexity of the fuel's inorganic chemistry (including the original mode of occurrence of the various elements), and the observed oxygen fugacity. Pyrochemical environments vary from reducing to oxidizing as a result of proximity to the flame and operational mode (combustion versus gasification). Consequently, multivalent elements further contribute to the complexity of slag/ash behavior by essentially behaving as separately unique elements when in their various valence states. In coal, the two abundant, multivalent inorganic elements are Fe (0, + 2, and +3) and S (−2, 0, +2, +4, and +6). In petroleum there are four abundant, multivalent inorganic elements: Ni (0 or +2), Fe (0, +2, and +3), V (+2, +3, +4, and +5), and S (−2, 0, +2, +4, and +6). The larger number of abundant inorganic elements in petroleum than coal, as well as the broader range of associated valence states, leads to more diverse slag/ash species formed during petroleum combustion/gasification, and consequently less predictable slag/ash behavior. A phase characterization of slags produced by the gasification of petroleum coke (a petroleum refining byproduct) illustrates their increased complexity with respect to typical coal slags.     

Geochemical modes of organic system and paragenesis of microelements in coal

The paragenesis of microelements in coal signifies their concentration together within the organic system, which is associated with the formation of organic compounds and authigenic minerals. Interest focuses on the geochemical environments: in particular, the oxygen, carbonate, hydrogen-sulfide, and chloride environment, as characterized by the activities of the corresponding components. The concentration of microelements in such environments is analyzed. In each set of conditions, the paragenesis of microelements strongly bound to the organic and mineral masses will be different.     

Associations and parageneses of microelements in coal

Microelements present in coal may be chemically bound with organic matter or with mineral impurities (clastic and authigenic minerals). Analytical data present the total (gross) content of microelements in coal. Such microelements are generally present in associations. In addition, some chemical elements accumulate in the coal on account of their content in organic matter; they constitute a paragenesis. In predicting the content of rare metals in coal deposits and in their extraction from the coal, it is important to establish the parageneses of the microelements—in other words, to distinguish the parageneses from associations of microelements. Such microelements may create anomalous concentrations in the coal. The present work establishes the characteristics of associations and parageneses of microelements in coal and proposes a statistical method for distinguishing parageneses from associations. The method is illustrated for data regarding Baikal coal deposits; it proves very effective.     

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.     

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.     

Reaction studies of an Egyptian coal under combustion-related conditions by thermal analysis-mass spectrometry

Thermal analysis-mass spectrometry (TA-MS) has been used to study the reactions of Al Maghara coal and its low temperature ash (LTA) under combustion-related conditions. The TA-MS profile of the coal gives information on combustion performance (ignition, peak combustion and burnout temperatures) and on chemical changes to the volatile matter (H₂O, SO₂, CO₂ and NO₂), char and minerals. X-ray diffraction identified pyrite as the major mineral component in the coal. The major and only feature of the TA-MS profile of the LTA is SO₂ evolution associated with decomposition of pyrite and iron sulphates. The high sulphur content of Al Maghara coal is a severe obstacle to its use in combustion. Cleaning of the coal to reduce the sulphur to an acceptable level is considered to be essential.     

宣化煤田泥岩特征分析及聚煤规律

文章通过分析宣化区泥岩的成分、微量元素及泥岩类型等特征,得出结论:该区泥岩主要形成弱碱性弱还原下的内陆淡水湖泊中。这对恢复该区古环境和掌握煤系的聚煤规律着非常重要的意义。     

Centrifugal float–sink separation of fine Turkish coals in dense media

Zonguldak bituminous coal, Tunçbilek and Soma–Merkez lignites were each separated into two sub-fractions, coal rich and mineral matter rich, using a centrifugal float–sink separation technique in heavy media. An isopropyl alcohol (IPA)–carbon tetrachloride (CCl₄) mixture and a zinc chloride (ZnCl₂) solution, with a specific gravity of 1.40 g cm⁻³ at 25°C were used as dense medium liquids. The addition of surface active agents (Triton X-100 and Brij-35) to the zinc chloride solution improved the removal of minerals. The recovery and purity of the final product (float) obtained from the heavy media separation depend on such parameters as the density of the medium, rotor speed and centrifugation time. The separation efficiency of each coal differed significantly. Particle size distributions of the coals and their float and sink fractions were analysed using a Laser Particle Size Analyser. A Scanning Electron Microscope (SEM) was used to interpret the liberation of minerals from the coal particles.     

Mineralogy of combustion wastes from coal-fired power stations

A combination of methods, including separation procedures, light microscopy, SEM, TEM, XRD and DTA-TGA methods, were used to characterize the phase-mineralogical and chemical composition, microstructural and some genetic phase peculiarities of solid waste products from coal burning. Fly ashes, bottom ashes and lagooned ashes from eleven Bulgarian thermoelectric power stations were studied. These products comprise inorganic and organic constituents. The inorganic part consists mainly of non-crystalline (amorphous) components and lesser amounts of crystalline components represented by various major, minor and accessory mineral phases. The organic constituent contains unburnt coal components represented by slightly changed, semicoked and coked coal particles. The origin of solid phases could be: primary — minerals and phases contained in coal and having undergone no phase transition (silicates, oxides, volcanic glass, coal particles); secondary — phases formed during burning (magnetite, hematite, metakaolinite, mullite, anhydrite, lime, periclase, CaMg silicates, glass, semicoke, coke); or tertiary — minerals and phases formed during the transport and storage of fly ashes and bottom ashes (sulphates, carbonates and oxyhydroxides).     

Distribution of trace elements in coal from the Powhatan No. 6 mine,Ohio

Size and density separates of low-temperature-ashed coal from the Powhatan No. 6 mine, Ohio, have been used to determine the mode of occurrence of 28 minor and trace elements in coal. The size distribution of the major minerals has been determined, and correlations of trace elements with major minerals have been made. The role of minor minerals in the mode of occurrence of trace elements is also discussed. Instrumental-neutron-activation analysis was used to determine elemental concentrations, and X-ray diffraction and scanning electron microscopy were used for mineral identification.     

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.     

Comparative chemical and mineral characterization of some Bulgarian coals

The mineralogy and chemical composition of lignitic, subbituminous and bituminous coal and coal-ash samples from six Bulgarian deposits, namely Maritza West (MW), Sofia (S), Maritza East (ME), Bobov Dol (BD), Pernik (P) and Balkan (B), were studied and a model for comparative characterization of their composition was done. Major minerals identified in the crystalline matter of Bulgarian coals are commonly quartz, kaolinite, illite, calcite, pyrite, plagioclase, K-feldspar and gypsum and occasionally dolomite, siderite, Fe oxyhydroxides and Fe sulphates. Some genetic features of the inorganic matter in coal and coal ash are described and compared. The coals studied show high detrital (P, B, BD, ME) or high authigenic (S, MW) mineral abundance with sulphide–sulphate (P, BD, ME, MW) or mixed carbonate and sulphide–sulphate (B, S) authigenic mineral tendencies. The high-temperature ashes of these coals belong to sialic (P), sialoferricalcic (B, BD), sialoferric (ME) or ferricalsialic (MW, S) chemical types. They have high (B, P, BD) or low (ME, MW, S) silicate mineral abundance with sulphate (B, P, ME, MW, S) or oxyhydroxide (BD) mineral tendencies.     

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.     

Analysis of sub-micron mineral matter in coal via scanning transmission electron microscopy

The fine-scale mineral matter in three US coals has been analysed via scanning transmission electron microscopy (STEM). The samples observed were a North Dakota lignite, a Kentucky bituminous, and a Pennsylvania semi-anthracite. Specific mineral types, differing among the three coals examined, appear to predominate at this fine size scale (particles ? 200 nm in diameter). Fe-rich and Ba-rich minerals in the lignite, a Ti-rich mineral in the bituminous and Ca-rich and Ti-rich minerals in the semianthracite were the predominant species found. The inherent mineral content in the observed organic background also differed from coal to coal. The distributions of mineral species in the size range ? 200 nm reported herein do not reflect the distributions in the larger size ranges obtained by more macroscopic techniques.     

Trace elements in coal: Associations with coal and minerals and their behavior during coal utilization - A review

Trace elements such as mercury, arsenic and selenium present in coal are known to be of concern for public health. Coal-fired power plants have resulted in emission of several tons of TEs in environment. These elements mostly evaporate during combustion and condense either homogeneously as sub-micron ash or heterogeneously onto already existing fine ash. The coal-mineral and mineral-mineral associations play an important role in the formation of fine particles and in subsequent condensation of trace elements in various phases. Any retention of these elements in fly ash particles is strongly influenced by their association with other minerals in individual coal and mineral grains. Clean coal technology development is, therefore, a priority area for research and needs continuous improvements in increased efficiency and decreased pollutant emission. The paper will include trace elements in different coals from around the world. It will consider different modes of occurrences present in coals, the ash formation and evaporation of trace elements and emissions. The typical emissions from typical power stations will be presented. The paper will also review different approaches adopted in estimating the deportment of these elements. The paper at the end would discuss control strategies for reducing emissions and future directions.     

Oxygen in coal ash: a simplified approach to the analysis of ash and mineral matter in coal

Oxygen was determined accurately in eight U.S. Bureau of Mines coal ash samples A, B, D, F, G, I, and J, NBS coal fly ash 1633 reference material, and two low-temperature ashes (LTA) from lllinois State Geological Survey. The method uses fast-neutron activation (FNA) analysis employing a dual counting and irradiation system which is essentially free from interferences. The stoichiometric balance based on analyses of the ashes performed by the USBM is calculated and summations given in oxide and element percent. Excellent agreement is found with the chemical data obtained by classical silicate analysis methods. Accurate oxygen determination for coal ash and LT-ash (or mineral matter) is important for calculation of data in the ultimate analysis of coal as such. Knowledge is required for recalculation of the data on a dry and dry-ash-free basis. The routinely used ‘oxygen by difference’ values are inadequate for accurate work. In order to determine the organic oxygen in coal one also has to correct for oxygen in mineral matter and oxygen in the water removed as moisture. The Parr formula and other methods of empirical estimation are inadequate and may be replaced in some cases by the oxygen determination. The complete data provide a quantitative basis for stoichiometric interpretation of coal analyses. It was found that the eight coal-ash samples analysed contained 45.5 ± 3% oxygen. Since these ashes represent a large variety of U.S. coals, this figure can be used as an estimate for recalculation and evaluation of the proximate and ultimate coal analyses. It is better, however, to use values actually determined in ash by the rapid fast-neutron activation method. This permits a better estimation of the sum of cations plus sulphates in the ash.     

Trace element affinities in two high-Ge coals from China

The Lincang (Yunnan Province, Southwest China) and Wulantuga (Inner Mongolia, Northeast China) coal deposits are known because of the high-Ge content. These coals have also a high concentration of a number of other elements. To determine the mode of occurrence of the enriched elements in both coals, six density fractions from <1.43 to >2.8 g/cm³ were obtained from two representative samples using heavy-liquids. A number of peculiar geochemical patterns characterize these high-Ge coals. Thus, the results of the chemical analysis of these density fractions showed that both coals (very distant and of a different geological age) are highly enriched (compared with the usual worldwide coal concentration ranges) in Ge, As, Sb, W, Be, and Tl. This may be due to similar geochemistry of hydrothermal fluids influencing the Earth Crust in these regions of China. Moreover, Wulantuga coal (Early Cretaceous subbituminous coal) is also enriched in Ca, Mg, and Na, and Lincang coal (Neogene subbituminous coal) in K, Rb, Nb, Mo, Sn, Cs, and U. A group of elements consisting of Ge, W, B, Nb, and Sb mostly occur with an organic affinity in both coals. Additionally, Be, U, and Mo (and partially Mn and Zn) in Lincang, and Na and Mg in Wulantuga occur also with a major organic affinity. Both coals have sulfide-arsenide mineral assemblages (Fe, S, As, Sn, and Pb, and in addition to Tl, Ta, and Cs in the Lincang coal). The occurrence of Al, P, Li, Sc, Ti, V, Cr, and Zr in both coals, and Ba in Lincang, are associated with the mineral assemblage of silico-aluminates and minor heavy minerals. Furthermore, P, Na, Li, Sc, Ti, Ga, Rb, Zr, Cr, Ba, Th, and LREE (La, Ce, Pr, Nd, and Gd) in Lincang are associated with mineral assemblages of phosphates and minor heavy minerals. The two later mineral assemblages are derived from the occurrence of detrital minerals. Finally, the two coal samples have also the sulfate mineral assemblage (Ca and Sr) that probably occur as a consequence of a diagenetic oxidation and alteration of the coal seams. The enrichment of Ge in coal occurred when the organic matter was still reactive to trap Ge, but several features indicate that the enrichment was diagenetic.