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At least 1,441 records · Page 80Linked to original sources

Correlation of natural gas content to iron species in the New Albany shale group

Mössbauer parameters were obtained for four Illinois Basin shales and their corresponding < 2μm clay fractions from wells drilled through the New Albany Shale Group in Henderson, Tazewell, and Effingham counties in Illinois and Christian County in Kentucky. Off-gas analysis indicated that the Illinois cores were in an area of low gas potential, while the Kentucky core was in an area of moderate-to-good potential. Iron-rich dolomite (ankerite) was found in the Kentucky core but not in the Illinois cores. In the Kentucky core, gas content could be correlated with the ankerite in the bulk sample, the Mössbauer M (2) species in the clay fraction, and a ferrous iron species in the clay fraction. The location of the greatest concentration of natural gas in the Kentucky core could be predicted by following the changes in percentage concentration of these iron species when plotted against the depth of burial of the core sample.

Illinois, Kentucky↗

Ferromagnetic and superparamagnetic contamination in pulverized coal

Although no significant major-element contamination is introduced by grinding coal in a steel pulverizer, abraded steel particles can conceivably affect the magnetic properties of pulverized coal. Magnetic and scanning-electron-microscope analyses of pulverized coal and coal fragments from the Herrin No. 6 seam in Illinois showed ferromagnetic and superparamagnetic contamination from the grinder. Significant changes in the magnetic properties of the coal were noted, indicating a total steel contamination of approximately 0.02 wt%. When coal samples were vibrated in the magnetic field of the vibrating-sample magnetometer, the superparamagnetic steel particles moved through the pulverized coal, and participated in the formation of multidomain clusters that in turn substantially affected the magnetization of the coal.

Illinois↗

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.

Ohio↗

Chemical oxidation of anthracite with hydrogen peroxide via the Fenton reaction

Solutions of 30% H 2 O 2 ranging from pH = 0 to pH = 11.5 have been used to oxidize anthracite at room temperature. The inorganic impurities, primarily pyrite, catalysed the oxidation and reduction of H 2 O 2 (the Fenton reaction) to form the hydroxyl radical; the oxidation of the organic matter was minimal and was observed only in strong acidic solutions ( pH < 1.5). After acid demineralization, samples of the same anthracite underwent a significant enhancement of oxidation in both acid and alkaline solutions ( pH = 0.4–11.5). As all the iron had been removed from the surface and the reactions were completed in a much shorter time, the oxidation mechanism must have been of a different nature than that for the untreated anthracite. A qualitative model based on the catalytic decomposition of H 2 O 2 by activated carbon sites in the coal surface is used to explain the oxidation of the demineralized anthracite.

Fuel↗

Oxidation of pyrite in coal to magnetite

When bituminous coal is heated in an inert atmosphere (He) containing small amounts of oxygen at 393–455 °C, pyrite (FeS 2 ) in coal is partially converted to magnetite (Fe 3 0 4 ). The maximum amount of Fe 3 0 4 formed during the time of heating corresponds to 5–20% of the total pyrite present, depending on the coal sample. The magnetite forms as an outer crust on the pyrite grains. The fact that the magnetic properties of the pyrite grains are substantially increased by the magnetite crust suggests that pyrite can be separated from coal by use of a low magnetic field. In a laboratory test, 75% removal is obtained by means of a 500 Oe magnet on three samples, and 60% on a fourth sample.

Fuel↗

Sulphur in char and char desulphurization by acid leaching and hydropyrolysis

Sulphur compounds volatilized during pyrolysis of acid-leached char were measured to determine characteristics of char desulphurization reactions. Pyrolysis of char in a hydrogen atmosphere (hydropyrolysis) produced a much higher concentration of thiophenic organics compared with that produced during pyrolysis in a nitrogen atmosphere. Hydrogen sulphide gas evolution, at progressively increasing pyrolysis temperature in a helium atmosphere, was measured on five char samples: untreated char, hydrochloric acid-leached char, and three model chars: a demineralized char and two demineralized chars incorporated with sulphur via reactions with elemental sulphur. Hydrogen sulphide gas evolution in untreated char and acid-leached char was found to peak in three temperature regions; the maxima are thought to relate to sulphur in different bonding environments. The amounts of hydrogen sulphide volatilized were much higher for acid-leached char than for untreated char. The gas evolved from each of the remaining three samples showed a single peak region corresponding closely to one of the three peak regions observed for the first two chars. The results of this study indicate that elemental sulphur was produced during hydrochloric acid leaching of the untreated char and suggested that the improved rate of desulphurization observed in the char that had been acid-leached before hydropyrolysis was due in part to the conversion of strongly bound mineral sulphur forms to more weakly bound sulphur forms that are predominantly elemental sulphur in character, and are more easily removed by hydrogen.

Fuel↗

Secretinite: A proposed new maceral of the inertinite maceral group

The new maceral secritinite (name derived from the word ‘secretory’) is proposed for subcircular, ovoid, crescent-shaped or oblong, commonly round on one or more sides, noncellular, highly reflective components of the inertinite maceral group. This maceral of secretory origin, known from many bituminous coals throughout the world, has been confused with cellular, opaque fungal masses of high reflectance. It is suggested that these fungal masses be assigned to the previously proposed maceral funginite of the inertinite maceral group. The maceral term ‘sclerotinite’ and maceral-varietal terms ‘fungo-sclerotinite’ and ‘resinosclerotinite’ should be abandoned because they confuse the natural botanical relations and because they are unnecessary if the proposed maceral names, secretinite and funginite, are accepted. The maceral-varietal terms secreto-macrinite and secreto-inertodetrinite are proposed for angular to irregular constituents whose properties are physically gradational from secretinite into the macerals macrinite and inertodetrinite.

Fuel↗

Correlation between electron spin resonance spectra and oil yield in eastern oil shales

Organic free radical spin concentrations were measured in 60 raw oil shale samples from north Alabama and south Tennessee and compared with Fischer assays and uranium concentrations. No correlation was found between spin concentration and oil yield for the complete set of samples. However, for a 13 sample set taken from a single core hole, a linear correlation was obtained. No correlation between spin concentration and uranium concentration was found.

Alabama, Tennessee↗

Oxidation of pyrite in an anoxic atmosphere

Pyrite (FeS 2 ) inclusions in coal, when heated in an oxygen deficient atmosphere (approximately 1% oxygen), become coated with magnetic Fe 3 O 4 due to oxidation. Most of the FeS 2 can thus be removed from the coal by magnetic separation to reduce the sulphur concentration. The oxidation products have been studied in greater detail by measuring the SO 2 and O 2 in the effluent gas during the heating process and by performing further magnetic measurements. At 582 K, the pyrite surface was oxidized to FeSO 4 . Significant oxidation of FeSO 4 and FeS 2 to Fe 3 O 4 was observed starting at 677 K. At about 681 K, the Fe 3 O 4 is further oxidized to α-Fe 2 O 3 . At 681 K, under isothermal conditions, the oxidation is impeded by the α-Fe 2 O 3 formed on the surfaces of the grains. If the temperature is rapidly increased, the oxygen penetrates the α-Fe 2 O 3 veneer to the FeS 2 core of the pyrite grains and oxidizes essentially the whole pyrite mass to Fe 3 O 4 before α-Fe 2 O 3 can be formed.

Fuel↗

Use of stable sulphur isotopes to monitor directly the behaviour of sulphur in coal during thermal desulphurization

A method has been developed using stable sulphur isotope analyses to monitor the behaviour of sulphur forms in a coal during thermal desulphurization. In this method, the natural stable isotopic composition of the pyritic and organic sulphur in coal is used as a tracer to follow their mobility during the desulphurization process. This tracer method is based on the fact that the isotopic compositions of pyritic and organic sulphur are significantly different in some coals. Isotopic results of pyrolysis experiments at temperatures ranging from 350 to 750 °C indicate that the sulphur released with the volatiles is predominantly organic sulphur. The pyritic sulphur is evolved in significant quantities only when pyrolysis temperatures exceed 500 °C. The presence of pyrite seems to have no effect on the amount of organic sulphur evolved during pyrolysis. The chemical and isotopic mass balances achieved from three different samples of the Herrin (No. 6) coal of the Illinois Basin demonstrate that this stable isotope tracer method is quantitative. The main disadvantage of this tracing technique is that not all coals contain isotopically distinct organic and pyritic sulphur.

Illinois, Indiana, Kentucky↗

Pyrolysis g.c.-m.s. of a series of degraded woods and coalified logs that increase in rank from peat to subbituminous coal

Xylem tissue from degraded wood and coalified logs or stems was examined by pyrolysis g.c.-m.s. to improve understanding of the coalification process. The pyrolysis data, when combined with solid-state 13 C n.m.r. data for the same samples, show several stages of evolution during coalification. The first stage, microbial degradation in peat, involves the selective degradation of cellulosic components and preservation of lignin-like components. As coalification increases, the lignin structural units undergo a series of defunctionalization reactions. The first of these involve loss of methoxyl groups, with replacement by phenolic hydroxyls such that catechol-like structures are produced. As the xylem tissue is converted to subbituminous coal, the persistence of phenols and methylated phenols in pyrolysis g.c.-m.s. data of subbituminous coal suggests that the catechol-like structures are being converted to phenol-like structures. The ability to discern detailed changes in the chemical structural composition of a genetically and histologically related series of samples provides an ideal method for developing models of coal structure, especially that of low-rank coal.

Fuel↗

Microbial oxidation of pyrrhotites in coal chars

The ability of Thiobacillus ferrooxidans to oxidize pyrrhotite minerals occurring in coal chars was investigated, to evaluate the feasibility of microbial char desulphurization. Bio-oxidation of pyrrhotites in chars produced by two different processes was demonstrated conclusively. Microbial removal of sulphur from a char and its parent coal proceeded at the rate of 3.5% and 12% day −1 , respectively with a total of 48% and 81% removal after 27 days. The pH of shake flask cultures containing the coal dropped naturally to a final value of 2.2, while the pH of cultures containing the corresponding char rose and had to be lowered artificially with additional acid. Amending char cultures with elemental sulphur to increase acidity upon bio-oxidation and prevent precipitation of ferric iron was successful; however, the extent of pyrrhotite removal, as demonstated by X-ray diffraction analysis, was not improved. As yet, there is no explanation for the failure of microbial removal of pyrrhotitic sulphur to go to completion.

Fuel↗

The laser microprobe mass analyser for determining partitioning of minor and trace elements among intimately associated macerals: An example from the Swallow Wood coal bed, Yorkshire, UK

A study of the elemental composition of intimately associated coal macerals in the English Swallow Wood coal bed was conducted using a laser microprobe mass analyser, and indicated a similar trace and minor elemental chemistry in the vitrinite and cutinite and a different elemental signature in the fusinite. Three to six sites were analysed within each maceral during the study by laser micro mass spectrometry (LAMMS). Al, Ba, Ca, Cl, Cr, Dy, F, Fe, Ga, K, Li, Mg, Na, S, Si, Sr, Ti, V, and Y were detected by LAMMS in all three macerals but not necessarily at each site analysed. The signal intensities of major isotopic peaks were normalized to the signal intensity of the m z "> mz 85 peak (C 7 H) to determine the relative minor- and trace-element concentrations among the three dominant macerals. The vitrinite and the cutinite were depleted in Ba, Ca, Dy, Li, Mg, Sr, and Y relative to their concentrations observed in the fusinite. The cutinite was distinguished over vitrinite by less Ti, V, Cr and Ca, and K Ca $ &#x306; 1 "> KCa$1 (relative signal intensities). The fusinite, relative to the cutinite and vitrinite, was relatively depleted in Cr, Sc, Ti, and V. The fusinite, as compared with both the cutinite and vitrinite, was relatively enriched in Ba, Ca, Dy, Li, Mg, Sr, and Y, and also showed the most intense m z "> mz 64, 65, 66 signals (possibly S 2 + , HS 2 + , H 2 S 2 + , respectively). The LAMMS data indicate a common source for most elements and selective loss from the maceral precursors in the peat or entrapment of certain elements as mineral matter, most likely during the peat stage or during early diagenesis. The relatively high amounts of Ba, Ca, Dy, Li, Mg, Sr, and Y in the fusinite are consistent with micron and submicron mineral-matter inclusions such as carbonates and Ca-Al phosphates (probably crandallite group minerals). Mineralogical data on the whole coal, the LAMMS chemistry of the vitrinite and cutinite, and scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDAX) of the elements in the macerals are consistent with the presence of micron and submicron inclusions of clays such as kaolinite, illite, and Ca-rich or Ca-bearing minerals (e.g. calcite, Ca-Al phosphates, and illite) which are different in kind and proportions in the three macerals. The variance as measured by the F -statistic for all three macerals indicates generally a nonuniform distribution of minor and trace elements in all three macerals, thus supporting a mineral-matter (inorganic) origin of the elements analysed. Exceptions are Al, K, Fe, Ga, and Sr in the vitrinite and cutinite, which is consistent with organic complexing or a uniform distribution of micron or submicron mineral matter such as illite and phosphate(s).

Yorkshire↗

Superparamagnetic Fe 3 O 4 particles formed by oxidation of pyrite heated in an anoxic atmosphere

As a follow-up to previous gas analysis experiments in which pyrite was heated to 681 K in an anoxic (oxygen starved) atmosphere, the first oxidation product, FeSO 4 , was studied as a bulk material. No decomposition of FeSO 4 to Fe 3 O 4 was observed in the temperature range studied. The lack of decomposition of bulk FeSO 4 to Fe 3 O 4 suggests that FeS 2 oxidizes directly to Fe 3 O 4 , or that FeSO 4 , FeS 2 and O 2 react together to form Fe 3 O 4 . Magnetic susceptibility and magnetization measurements, along with magnetic hysteresis curves, show that small particles of Fe 3 O 4 form on the pyrite surface, rather than a continuous layer of bulk Fe 3 O 4 . A working model describing the oxidation steps is presented.

Fuel↗

Carbon monoxide detection of chemisorbed oxygen in coal and other carbonaceous materials

The oxidation of carbon monoxide by mildly oxidized and devolatilized coal samples was studied thermogravimetrically. The oxidation was attributed to oxygen chemisorbed on inorganic components of the coals. The reaction of CO with pyrite producing carbonyl sulphide, OCS, accompanied the oxidation. A mechanism for CO oxidation is proposed in which active oxygen chemisorbed on the inorganic components of the coal directly oxidized CO to CO 2 , and facilitates the chemisorption of CO on the coal as carbonate. A factor, &#x3B1; = ( 11 14 ) [1 &#x2212; ( W n W c )] "> α = (1114) [1 − (WnWc)] , was derived where W n is the sample weight loss not attributed to OCS formation, and W c is the estimated weight of evolved CO 2 . This quantity is proportional to the fraction of CO 2 produced by the direct oxidation of CO, and was used to compare the coal samples studied. Samples of an Illinois No. 5 coal yielded average α values of 0.7 and those of an Illinois No. 6 coal yielded values of 0.6, indicating that in these cases, the majority of CO 2 produced came from the direct oxidation of CO. The results obtained for the coal samples are compared with a selection of carbonaceous samples for which the proposed mechanism does not apply.

Fuel↗

Inorganic ground-water chemistry at an experimental New Albany Shale (Devonian-Mississippian) in situ gasification site

Experimental in situ gasification of New Albany Shale (Devonian-Mississippian) has been conducted in Clark County. Analyses of ground water sampled from a production well and nine nearby monitoring wells 3 months after a brief in situ gasification period revealed changes in water chemistry associated with the gasification procedure. Dissolved iron, calcium and sulphate in ground water from the production well and wells as much as 2 m away were significantly higher than in ground water from wells over 9 m away. Dissolved components in the more distant wells are in the range of those in regional ground water. Thermal decomposition of pyrite during the gasification process generated the elevated levels of iron and sulphate in solution. High concentrations of calcium indicate buffering by dissolution of carbonate minerals. While iron quickly precipitates, calcium and sulphate remain in the ground water. Trends in the concentration of sulphate show that altered ground water migrated mostly in a south-westerly direction from the production well along natural joints in the New Albany Shale.

Indiana↗