Possibilities of the utilization of micropetrographic parameters in the scientific classification of bituminous coals

Proposals for new scientific classifications of bituminous coals are based on micropetrographic parameters, i.e. vitrinite reflectance as a criterion of the coalification and maceral composition, presupposed to express the connection between the genetic peculiarities and physical, chemical, and technological properties of the coal mass. In the case of coals with high inertinite contents, however, the utilizability of these parameters meets with difficulties resulting from the subjectivity of determining the different transitional material and from insufficient knowledge of inertinite behaviour at higher temperatures. In the case of the maceral-variable bituminous coals produced in the Ostrava-Karviná Coal Basin, these insufficiencies are not important since it is especially the expression of the variability of the properties of isometamorphic vitrinites, which has decisive effects up-on the course of the thermo-chemical transformations, that is of principal importance to the scientific classification of these coals.In the first approximation, the properties of isometamorphic vitrinites may be expressed by the parameter (H/O)_at, closely connected with fluidity. While the micropetrographic parameters reflect in particular the peculiarities in the chemical structure of the aromatic parts of coal macromolecules, the parameter (H/O)_at expresses the properties of the non-aromatic structures of vitrinite, significantly affecting the course of its thermal degradation. The experimental results show that the value of the parameter (H/O)_at, fluidity and the course of degassing the coal of a lower coalification are independent of the maceral composition and vitrinite reflectance; also that the caking and coking properties of low-rank coals are especially dependent on the parameter (H/O)_at and partially on the micropetrographic parameters. All these facts should be taken into consideration in preparing new scientific classifications of bituminous coals.     

Observations on low-temperature oxidation of minerals in bituminous coals

Mineral matter in three naturally weathered coals from Pennsylvania strip mines and in two laboratory-oxidized coals has been characterized by ⁵⁷Fe Mössbauer spectroscopy, scanning electron microscopy and other techniques to determine mineralogical trasnformations that occur in coals during weathering. Pyrite was found to be the most readily oxidized mineral, forming a variety of iron sulfates initially and geethite eventually. The iron sulfates formed were different in the two laboratory-oxidized coals, despite identical oxidation treatments. Calcite disappeared from one calcite-rich coal with increasing oxidation, but was not replaced by an equivalent amount of gypsum. A severely weathered strip-mine coal was enriched in calcium, which was dispersed through the oxidized macerals. Extended X-ray absorption fine-structure spectroscopy indicated that this dispersed calcium was most likely present as salts of carboxylic acids. Siderite was suprisingly resistant to oxidation at room temperature. Less direct evidence indicates that clay minerals also take part in the alteration to some extent.The coals oxidized in the laboratory showed alteration behavior that differed in a number of respects from that of the strip-mine coals. For example, iron sulfates were much less common in the latter coals; also, the formation of geothite appeared to be controlled to a large extent by the pyrite particle size in the strip-mine coals, but not in the laboratory-oxidized coals.The oxidation of an individual pyrite grain is not only a function of general conditions (temperature, humidity, oxygen partial pressure), but also the immediate local (< 1 mm) chemistry, as a variety of iron sulfates were observed in the coals, often in close proximity. Also, assemblages of gypsum and goethite were observed in otherwise slightly oxidized coal, which indicates that the alteration of pyrite and calcite, when in close contact, proceeds most rapidly.     

Deformation metamorphism of bituminous and anthracite coals from China

Tectonic displacement of coal seams in China has resulted in faulting parallel to coal bedding. Displacement along these faults caused significant comminution of the coal on the footwall contributing to various mining problems, the worst of which is catastrophic failure, or “outbursting” of the working face during mining. The granular texture and mostly unconsolidated nature of the coal suggests that faulting occurred relatively late in the coalification sequence, at a time of maximum tectonic stress. Coal samples taken on either side of the fault plane (normal and deformed coal layers) were obtained in an effort to establish what influence these tectonic stresses might have had on coal properties as well as what they might reveal about the influence of tectonic pressure on organic maturity. Sample sets were collected within coal beds from undisturbed and adjacent deformed layers, including 21 bituminous samples from the Pingdingshan coal field and nine anthracite samples from the Jiaozuo coal field, the Tieshenggou coal mine of the Yuxi coal field in Henan province, the Beijing Xishan coal field, the Baijiao mine of the Furong coal field in Sichuang province and the Baisha coal field in Hunan province, China. Results from vitrinite reflectance, proximate and ultimate analyses show some differences in reflectance, hydrogen content and nitrogen content of anthracite coal. No significant difference was found between volatile matter yields of normal and deformed coal specimens. GC measurements of the saturated hydrocarbon fraction of chloroform extracts from bituminous coals showed that lower molecular weight carbon fragments were concentrated in the deformed samples. Therefore, although changes in the gross chemical properties of the deformed coal were insignificant, some modification of the chemical structure is seen to have occurred as a result of exposure to tectonic pressure.     

Structural characterization of vitrinite-rich and inertinite-rich Permian-aged South African bituminous coals

Two South African coals of the same rank and age, but different in maceral composition were subjected to extensive structural analyses. Inertinite-rich Highveld coal (dominated by semifusinite) and vitrinite-rich Waterberg coal were studied to determine structural differences and similarities. The two coals had similar carbon content ( 84%, dmmf) and vitrinite reflectance (mean-maximum 0.71% for vitrinite-rich vs. 0.75% for inertinite-rich), but differed in hydrogen content (6.23% for vitrinite-rich and 4.53% for inertinite-rich). The inertinite-rich coal was more aromatic (86% for inertinite-rich and 76% for vitrinite-rich) and more polycondensed (indicated by a higher bridgehead carbon content). The inertinite-rich coal was structurally more ordered, with a higher degree of crystalline stacking. Both coals had similar average aromatic cluster sizes (16 carbons for vitrinite-rich and 18 carbons for inertinite-rich) and number of cluster attachments (6 attachments for vitrinite-rich and 5 attachments for inertinite-rich). Mass spectrometry showed that both coals consist of similar molecular weight distributions; ranging to approximately 1700 m/z with a maximum abundance of  450 m/z for the vitrinite-rich coal and  550 m/z for the inertinite-rich coal. Compared to the Argonne Premium coals the South African vitrinite-rich Waterberg coal was comparable to the coals in the high-volatile bituminous range and inertinite-rich Highveld was closer to the medium- to low-volatile bituminous range. Both coals were surprisingly similar in bulk characterization, although inertinite-rich Highveld coal was structurally more ordered, hydrogen deficient, and more aromatic.     

Statistical analysis in classification of bituminous coal

Hundreds of samples and 17 variables collected from coalfields of major coal-bearing strata over China except for Tibet and Taiwan, were used in this study. The dry, ash-free basis volatile matter (V ^r) and caking index (G _(RI)) were chosen by means of correlation analysis and stepwise discriminatory analysis as major indices of a new classification. By means of the optimum section, the boundary value of the axis of ordinate (G _(RI)) and axis of abscissas (V ^r) can be determined in the classification system. Thus, aV ^r –G _(RI) classification scheme diagram was formed and bituminous coal was divided into nine classes. Use of correspondence analysis reduced dimensions of sample-expressive space without losing initial information. The trend on the factor surface of samples shows that the classification obtained from correspondence analysis conforms to theV ^r –G _(RI) classification result and further verified the dependability of classification by two indices. At the same time, a certain relationship between the properties of a great variety of coal and their attributes can be explained. Hence, bituminous coal classification becomes more scientific, reasonable, and practical than before.     

Elemental concentrations and their distribution in two bituminous coals of different paleoenvironments

The vertical distributions of major and minor elements in two high-volatile bituminous coals of Eastern Tennessee are compared. The coals studied are the Pewee, deposited in a fresh-water environment, and the Upper Grassy Spring, previously thought to be influenced by a late incursion of marine water.X-ray fluorescence analyses were performed on a continuous series of specimens obtained from full-face channel samples representing the entire thickness of each seam. Correlation coefficients (r) for all element pairs show high positive correlations for element pairs normally associated with clay minerals. Equally good correlations were observed for (Si, Ti) and (Al, Ti), suggesting that titanium is associated with clay minerals in both coals. Strontium and phosphorous showed a high positive r factor for both the Upper Grassy Spring and the Pewee.Major differences were found to exist in the concentrations and distributions of sulfur, iron, and arsenic in the Upper Grassy Spring and Pewee seams. The Upper Grassy Spring contains an order of magnitude more sulfur than the Pewee as well as several times as much iron and arsenic. The element concentrations and especially their distributions in the Upper Grassy Spring suggest an earlier time for the marine incursion than previously reported. In fact, there is evidence that this coal deposit may have been influenced by marine conditions from its inception.     

Interactions between organic matter and minerals in two bituminous coals of different rank

The association between specific mineral and organic constituents in two Asturian bituminous coals of different rank was studied. For this, raw coals were fractionated by density and the variation of a number of parameters was followed in parallel. Results of coal chemical analyses, including analyses for 22 elements, were used to establish the elemental association with coal organic matter. Petrographic analyses determined the distribution of macerals among densimetric fractions, vitrinite reflectance being at a minimum in the intermediate density fractions. Mineral species were identified by X-ray diffraction, FT-IR spectroscopy and Mössbauer spectroscopy. Comparison of trends for different parameters determined using this set of techniques allowed classification of the various minerals according to their association with organic matter. Carbonates seem to be specifically associated with the organic matter of the low-volatile bituminous coal whereas sulfides concentrate in the organic matter of the high-volatile bituminous coal. Vitrinite is the maceral exhibiting the most probable association with inorganic matter. The possibility of a merely physical association of fine-grained detrital minerals with organic matter cannot be excluded; nevertheless, one must bear in mind that even this type of interaction is important due to its effect on various coal preparation and utilization processes.     

Investigations on the petroleum generation potential of bituminous coals from the Saar region

The Saar basin contains bituminous coals (high volatile A and B). Five coals of Westphalian and Stephanian age with distinctly varying maceral compositions were analysed by Soxhlet extraction and supercritical extraction with different solvents and microscopically. From the data obtained it is concluded that the oldest coals have a potential for oil generation, whereas the younger coals do not. This conclusion is explained by varying liptinite contents and varying adsorption capacities of different vitrinite macerals for bitumen.     

The thermal decomposition studies of three Polish bituminous coking coals and their blends

The objective of this work was to investigate the thermal decomposition of various bituminous coal blends. Three Polish coals of varying rank (82.7, 86.2 and 88.7 wt.% carbon content) and caking ability (weak, moderate and strong) were collected from the Krupiński, Szczygłowice and Zofiówka mines, respectively. These coals were used to prepare binary and ternary blends. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used. The weight loss and heat flow during pyrolysis, and storage/loss elastic modulus measured as a function of increasing temperature were related to the caking ability of coals. Parameters determined with the TGA and the DSC methods in the binary and ternary blends were correlated with the proportion of strongly-caking-coal concentration in the blend. The weight loss of coal blends was found to be additive parameter. The DSC thermograms of binary blends were found to be different from those of the ternary blends, which suggests a different course for this blend pyrolysis.     

The joint effect of rank and grain size on the flotation of Australian bituminous coals

Laboratory batch flotation tests were carried out to determine the effect of grain size on the recovery of four Australian bituminous coals of high and low rank. The flotation concentrates, taken over successive time intervals, and the tailings, were sized and the recovery-size curves plotted. A method was developed for determining the proportions of liberated and composite grains in the various flotation products. Flotation tests were carried out in the presence of methylisobutylcarbinol (MIBC) and MIBC + kerosene. The shapes of the recovery-size curves depended on the rank of the coal and whether or not kerosene was present. The variation of the recovery with size was explained in terms of the joint effect of rank and size on the floatability of composite grains.     

A microscopic study of the combustion residues of subbituminous and bituminous coals from Alberta, Canada

Chars produced by the combustion of a set of three coals from Alberta, Canada, were classified morphologically using reflected light microscopy. Produced chars are different in morphological features, pore thickness, anisotropy and degree of reactivity, because of differences in the vitrinite and inertinite contents.The subbituminous A coal produced the highest percentage of unreactive or slightly reactive components due to its high inertinite content (20.0%), followed by isotropic cenospheres. Isotropic cenospheres, both thin- and thick-walled, and exploded cenospheres are the characteristic chars produced by the high-voltile bituminous B coal, whereas the low-volatile bituminous coking coal produced cenospheres with granular anisotropy (mosaic) on the walls and abundant coke fragmentsOptical microscopy is useful in differentiating the performance of a series of coals during combustion based on petrographic composition and rank and can aid in understanding the relationship between ‘reactive’ and ‘non-reactive’ coal macerals to burnout performance.     

Predicted CO2 emissions from maceral concentrates of high volatile bituminous Kentucky and Illinois coals

A large collection of well-characterized coals, documented in the Center for Applied Energy Research's (CAER) database, was used to estimate the CO₂ content of maceral concentrates from Kentucky and Illinois high volatile bituminous coals. The data showed no correlation between CO₂ versus coal ranks and between CO₂ versus maceral content. Subsequently, eight sets of low-ash density-gradient centrifugation (DGC) maceral concentrates from five coal beds were examined, spanning in the high volatile rank range. Heating value was not determined on the concentrates, but instead was calculated using the Mott–Spooner formula. There was a good correlation between predicted CO₂ and maceral content for the individual iso-rank (based on vitrinite reflectance, analyzed on whole (parent) coal) sets. In general, the predicted CO₂ increases from liptinite-rich through vitrinite-rich to inertinite-rich concentrates (note: no “concentrates” are absolutely monomaceral).     

Chemical composition of macerals in bituminous coals of the Gunnedah Basin, Australia, using electron microprobe analysis techniques

The chemical composition of the organic matter in the principal macerals of high-volatile bituminous coals from the Gunnedah Basin, New South Wales (Rv_max of telocollinite between 0.6 and 1.1%) has been evaluated from polished section specimens using an electron microprobe technique. Highest proportions of carbon occur in the inertinite macerals, especially fusinite and secretinite (formerly resino-sclerotinite), as well as in sporinite; lowest proportions of carbon occur in the different macerals of the vitrinite group. Oxygen shows the reverse trend, being most abundant in vitrinite and least abundant in the inertinite components, whereas sulphur is lowest in the inertinites and highest in the liptinite (mainly sporinite) present. Evaluations of maceral composition, using the carbon content of telocollinite as a rank indicator, show that carbon is more abundant in both sporinite and semifusinite, relative to vitrinite, in low-rank high-volatile bituminous coals. The difference decreases with increasing rank, and the proportion of carbon in telocollinite becomes essentially the same as that in sporinite and semifusinite at carbon contents of about 89 and 91%, respectively. The carbon content of fusinite and secretinite, on the other hand, does not seem to vary appreciably with rank advance. No significant difference in composition occurs in the rank range studied between the three vitrinite varieties present, desmocollinite, telocollinite and a more highly reflecting telocollinite resembling pseudovitrinite. No evidence was found to indicate a higher hydrogen content, relative to telocollinite, for the vitrinite matrix of desmocollinite.     

Secretinite—reflectance and chemical data from two high volatile bituminous coals (Upper Carboniferous) of North America

Secretinite—a maceral of the inertinite group as recognized by the ICCP in 1996—is a noncellular maceral of seed fern origin. New reflectance data indicate that this maceral has primary anisotropy with bireflectances of 0.4% to 0.9% in high-volatile B bituminous (Ro=0.6%) Carboniferous coal of North America. The highest reflectance is in cross-section as opposed to longitudinal section. Characteristic feature of secretinite is the virtual absence of Si and Al, unlike that in associated vitrinite. This indicates the absence of submicron aluminosilicates in secretinite and their presence in vitrinites. Secretinite is highly aromatic as indicated by low O/C ratios and high contribution of aromatic hydrogen bands detected by FTIR analysis.     

Resino-inertinites of Indian Permian coals — their origin, genesis and classification

Variously shaped discrete bodies with reflectance higher than the associated vitrinite occur in Permian coals in India, Australia and Africa and the Carboniferous coals of the United States, Canada and Europe. These bodies have been variously named by different authors. In the present paper they are described as ‘resino-inertinites’ as suggested by Lyons et al. (1982).Based on available information and our observations on Carboniferous and Permian coals, it is presumed that resino-inertinites were formed mainly from the resinous (resinite) and to some extent from the phlobaphinitic or corpocollinitic substances. Various morphological patterns developed on resino-inertinites have been interpreted to be governed by the chemical composition of their precursors and the degree of oxidation or fusinization during coalification. Influences of other vvariables viz., paleoenvironmental, paleodepositional, tectonic set up etc. on resino-inertinites are not clearly recognizable probably because all the previous effects were masked by subsequent fusinization.Different morphological features of resino-inertinites associated with early diagenetic and secondary mineralization have caused much confusion in their proper identification and classification. In order to resolve this problem, an attempt has been made to ascertain the source of resins in Indian Permian coals and their subsequent mode of transformation into resino-inertinites during coalification.Further, by critically evaluating morphological features of resino-inertinites and keeping the chemical nature of their precursors in view, a classification scheme has been proposed categorizing them into 3 types. The classification proposed may prove as a useful means for coal-seam correlation.     

Properties of altered coals associated with Carboniferous red beds in the Upper Silesian Coal Basin and their tentative classification

In the Czech and Polish parts of the Upper Silesian Coal Basin, red beds associated with the pre-Neoide tectonic structures are found. The occurrence of these beds is connected with changes in the development of the coal seams, in the macroscopic and microscopic character of coal and with its chemical and technological properties. These changes are due to the thermal and oxidation alteration of coal as a result of geological processes which, up to now, have not been clarified unambiguously. These altered coals were divided into groups according to their chemical and physical properties and vitrinite reflectance using statistical multicomponent methods. Coal samples classified as belonging to one of these groups correspond to a certain type of coal, characterized by a particular grade of thermal and oxidation alteration and petrographical composition.     

Structural investigations of Australian coals—IV. A characterization of the variation in rank of bituminous coal fractions by elemental analysis and I.R. spectroscopy

A series of seven Permian Australian bituminous coals of varying rank, were examined by quantitative infrared spectroscopy, using absorption coefficients K(cmmg^?1) and elemental analysis in the form of bond equivalence data. Both analytical techniques were found to be complementary in their average structural predictions. The coals were chemically fractionated into Total Solvent Extractables (T.S.E.), Solvent Extractable Humic Acids (S.E.H.A.) and insoluble Kerogens. Molecular condensation was found to decrease for the T.S.E. fractions, and increase as expected, for the insoluble kerogen fractions, as a function of increasing coal rank. The effect of aqueous base extraction upon the kerogen fraction, observable as an increase in oxygen by bond equivalence, could be related to minor changes in I.R. absorption coefficients and difference spectra.     

Volatile displacement of Meghalaya coals — A pointer to explore low sulphur coals

Volatile displacement, which measures the difference between calculated and experimental volatile matter, is indicative of abnormality in coals which may be related to petrological or chemical parameters. The volatile displacement (δυ) values of Meghalaya coals were calculated from their chemical analyses. Correlations of volatile displacement (δυ) with parameters such as carbon, hydrogen, moisture, oxygen, oxygen plus sulphate sulphur, oxygen plus pyritic sulphur, oxygen plus organic sulphur and total sulphur were studied. An approximately linear relationship exists only between δυ and moisture, and δυ and total sulphur, and not between other parameters. Plots on Seyler’s chart indicate the coals as perhydrous to orthohydrous. The linear relationship with total sulphur indicates that the coals may have become abnormal mainly due to the marine environment of deposition and weathering.     

Mercury-binding forms in coals and their geological provenances in coals of different types

Mercury (Hg) is an element of environmental and geological significance. Quantification of different Hg-binding forms is crucial to understand geological Hg provenances and associated geochemical processes during coal formation. In this study, seven coal samples were selected, according to coal rank (i.e., middle volatile bituminous, C-3; low volatile bituminous, C-2; anthracite, C-1), chemical anomalies (high S coal, IBC-105; high Cl coal, C22650) and sampling environment (fresh coal, LH; weathered coal LHW), to determine their Hg-binding forms using well-established sequential extraction procedures coupled with sink–float experiment. In the thermally metamorphosed samples C-1 and C-2, a comparative enrichment of total Hg relative to C-3 is observed. Silicate- and organic-bound Hg are the dominant Hg-binding forms in C-1, suggesting possible Hg sources from magma silicate and secondary Hg enrichment by adsorption. Sulfide- and organic-bound Hg are the most abundant Hg-binding forms in IBC-105, whereas only organic-bound Hg dominates in CC22650. Weathering processes are suggested to transform the abundant sulfide-bound Hg in LH to silicate- and organic-bound Hg in its weathering product LHW.