Storage of bituminous coals under argon

Two bituminous coals, crushed to < 0.32 cm ($\text{1}\text{8}$ in), have been stored for 455 days under argon at room temperature and examined for indications of oxidation. The only changes noted over this time were a 20–30% reduction in maximum fluidity from the Gieseler plastometer test for both coals, and conversion of 5% of the pyrite to iron oxyhydroxide in one coal. Although minor, these changes do indicate that more stringent conditions are necessary to minimize oxidation during long-term storage (>2 years).     

Fluidized-bed gasification of some Western Canadian coals

Three Western Canadian coals were gasified with air and steam in a fluidized bed of 0.73 mm sand and coal, at atmospheric pressure and temperatures of 1023–1175K to produce a low-calorific-value gas. One non-caking and two caking coals were tested. The effects of temperature, coal feed rate, $\text{air}\text{coal}$ ratio, $\text{steam}\text{coal}$ ratio, coal quality, coal particle size and bed depth on gas composition, gas calorific value and operating stability of the gasifier were established. Results are compared with those previously obtained for the same three coals when gasified in essentially the same equipment, but operated as a spouted bed.     

Heavy media separation of SRC-II feedstocks: 1. Effect on coal properties

The objectives of this investigation were to determine the effects of coal preparation on the properties of Run-of-Mine (ROM) and washed Powhatan and Ireland Mine coals and to assess the potential effects on SRC-II liquefaction yields. The effect of washing on the two coals was found to be quite similar. For both coals, the properties were altered more significantly by changes in separation media gravity than by changes in the coal size. The elemental composition of the Powhatan and Ireland washed coals was correlated with carbon content. It was shown that both the hydrogen and oxygen levels increased linearly with the carbon content of the coal samples. However, the $\text{H}\text{C}$ and $\text{O}\text{C}$ ratios were not changed significantly by coal cleaning. Only small variations in the nitrogen and organic sulphur levels were observed while the sulphate sulphur and chlorine levels were not affected by coal cleaning. The major impact of the coal cleaning was to reduce the pyritic sulphur (and hence the total sulphur) content of the coals. Most of the pyritic sulphur was shifted into the middling coal and refuse fractions while the clean coals had much lower contents and the pyritic sulphur level decreased with increasing carbon content. Coal cleaning did not significantly alter the maceral contents of vitrinite, exinite, total reactive macerals (TRM), or the reflectance of vitrinite; all these parameters varied over a very narrow range, probably within the precision of the measurement technique.     

Model for coal oxidation kinetics. 2. An effectiveness factor interpretation

Rate expressions are developed to describe the oxidation of coal in a fixed-bed reactor under conditions of significant diffusional effects. The model defines individual effectiveness factors for carbonic gas formation, oxygen deposition, and water production, to modify a chemical model derived previously. Experiments carried out on seven coals ranging in rank from lignite to bituminous to anthracite. All the coals exhibited particle size effects and the results fit the model in most cases to within ±10% both in the rate of overall oxidation and with respect to the individual reaction rates for several products. Activation energies and effectiveness factors were obtained for each coal and for each reaction. The effluent gas $\text{CO}{}_2\text{CO}$ ratio was found to be virtually constant for all five bituminous coals, being independent of reaction temperature, coal particle size, and oxygen partial pressure.     

Conversion of caking coal into non-caking coal by treatment with sulphur and sulphur dioxide

The effects on the caking properties of coals of reaction between the coals and S₈ and SO₂, have been studied. Caking coals (Akabira, Shinyubari, Zollverein, Indian Ridge, and Big Ben) lose their caking properties when treated with S₈ above 200 °C. For Shinyubari coal the crucible swelling number decreases from $\text{8}\text{1}\text{2}$ to 2 with treatment temperature of 235°C in which 5% of S is incorporated into the coal. The decaking of coal is attributed to thio-ether cross-linkages. Caking coals also lose completely their caking property when reacted with SO₂ at 170 °C. The decaking action of SO₂ is attributed to oxidation of coal in which ether cross-linkages are formed.     

Flash pyrolysis of coals: behaviour of three coals in a 20 kg h−1 fluidized-bed pyrolyser

Flash pyrolysis of Loy Yang brown coal, and Liddell and Millmerran bituminous coals has been studied using a fluidized-bed reactor with a nominal throughput of 20 kg h^?1. The apparatus and its performance are described. The yields of tar and hydrocarbon gases are reported for each coal in relation to pyrolysis temperature, as also are analytical data on the pyrolysis products. The peak tar yields for the dry, ash-free Loy Yang and Millmerran coals were respectively 23% wt/wt (at ≈ 580 °C) and 35% wt/wt (at $\text{\$}\text{?}$600 °C). The tar yield from Liddell coal was 31% wt/wt at ≈ 580 °C. Hydro-carbon gases were produced in notable quantities during flash pyrolysis; e.g. Millmerran coal at 810 °C gave 6% wt/wt (daf) methane, 0.9% wt/wt ethane, 6% wt/wt ethylene, and 2.5% wt/wt propylene. The atomic $\text{H}\text{C}$ ratios and the absolute levels of hydrogen in product tars and chars decreased steadily with increasing pyrolysis temperature.     

Mössbauer study of the thermal decomposition of FeS2 in coal

The Mössbauer effect has been used to study the transformations of FeS₂ in four different coals: IL No. 6, Ky $\text{9}\text{14}$, Blacksville No. 2, and Powhatan No. 5. The transformations of FeS₂ in the coals were studied in an inert atmosphere. It was observed that the pyrrhotites formed from FeS₂ have a considerable reduction in the isomer shift at 440 °C as compared to the values obtained in the absence of coal. This effect is associated with the interaction of the pyrrhotites with the coal constituents at high temperatures. There is also a significant line-broadening at 440 °C. This broadening is due either to vacancy motion in the iron sulphides and/or to motional broadening due to particle motion in the coal-derived liquids. The percentage conversion of pyrite to pyrrhotite depends markedly on time as well as type of coal. The weathering of the coal has a detrimental effect on the rate of conversion of pyrite to pyrrhotite. The ferrous sulphate layers covering the pyrite particles hinder the removal of sulphur from that surface. The major factor affecting the $\text{Fe}\text{S}$ ratio is the total amount of sulphur available for H₂S formation. Partial H₂S pressure is the crucial quantity controlling the stoichiometry of the pyrrhotites. Hence, a high percentage of H₂S in the reactor at high temperature will assure the formation of pyrrhotites with a high number of metal vacancies.     

Macerals in bituminous coals and the coking process: 2. Coal mass properties and coke mechanical properties

Bituminous coals produced in the Ostrava-Karviná coal basin show considerable variation in their maceral composition, vitrinite reflectance and fluidity. There is a close association of the latter with the $\text{H}\text{O}$ atomic ratio expressing the different chemico-structural properties of vitrinites of lower coalification. These properties of the coal mass all influence the coke mechanical properties; moreover the $\text{H}\text{O}{}_{\mathrm{at}}$ parameter is of principal importance to the course of the coking process. Laboratory, pilot-plant and full-scale experiments show that coals rich in inertinite may give cokes of suitable mechanical properties, providing the $\text{H}\text{O}{}_{\mathrm{at}}$, ratio and the bulk density are high enough. It should be noted, however, that these coals contain finely dispersed inertinite in the vitrinite mass and this may have a positive effect on the coke mechanical properties.     

Conversion of bituminous coal in COH2O systems: 3. Soluble metal catalysis

The oxyanions of the highest oxidation states of several transition metals, including W, Mo, Cr and Mn, were found to catalyse the liquefaction of Illinois No. 6 coal in $\text{CO}\text{H}{}_2\text{O}$ systems at 400°C. Unlike the high pH (s> 12) required in the base-catalysed system, the effective range for these metal-mediated conversions extend down to pH < 5.0. The benzene-soluble product was found to have a higher $\text{H}\text{C}$ ratio than the starting coal, and the metals were reduced to water-insoluble, lower oxidation states during conversion. A chain scheme is suggested as an explanation for the data.     

Flash pyrolysis of coals: influence of cations on the devolatilization behaviour of brown coals

The influence of cations on the pyrolysis behaviour of brown coals under flash heating conditions was investigated by means of a small fluidized-bed pyrolyser. A stream of coal particles in nitrogen was injected at rates of 1–3 g coal/h directly into a heated bed of sand fluidized by nitrogen. Yields of tar, C₁–C₃ hydrocarbons and total volatile matter from four Gelliondale brown coals and a Montana lignite were determined as a function of pyrolysis temperature. With all coals the maximum tar yield was obtained at 600 °C. Removal of cations present in the coals markedly increased the yields of tar and total volatile matter, with little effect on the yields of hydrocarbon gases. The converse was also observed in that the addition of Ca²⁺ to a cation-free coal decreased the yields of tar and total volatile matter. The extent of the reduction in tar yield at 600 °C in the presence of cations was found to be similar for all coals. After acid washing, tar yields appear to correlate with the atomic $\text{H}\text{C}$ ratios of the coals in a manner similar to that observed previously with bituminous coals.     

Electron paramagnetic resonance studies of South Wales coal

Nine South Wales coals of different rank and composition and seven structurally disturbed outburst prone coal samples were studied using electron paramagnetic resonance. An increase in baseline spin concentration with fixed carbon content was observed across the South Wales coalfield. Enhanced spin concentrations were observed for the structurally disturbed outburst prone coal samples. The $\text{g}$ value remained more or less constant with varying structural condition, fixed carbon, and volatile matter content of the coal.     

Photoacoustic microscopy of coal macerals

Photoacoustic microscopy, in which laser-light energy absorbed by coal macerals is converted into thermal energy, has recently emerged as an in-situ technique for coal maceral characterization. By employing two possible detection modes, different thermal properties can be measured and correlated with the material properties of the coal macerals. For the piezoelectric detection method, the photoacoustic signal is proportional to $\text{aB}\text{pc}$, where a is the coefficient of thermal expansion, B is the bulk modulus, p is the mass density, and c is the specific heat capacity of the maceral. The second method employs a gas microphone where the photoacoustic signal is proportional to $\text{l}\text{√Kpc}$, where K is the thermal conductivity. Photoacoustic data gathered by both methods on vitrinite and pseudovitrinite macerals from Appalachian basin coals agree with values predicted from known values of a, B, p and c. Data indicate that the thermal-elastic and thermal-conductance properties vary in a systematic manner from low- to high-rank coals. Throughout the entire rank range up to 92% carbon, vitrinite exhibits a significantly different photoacoustic response than pseudovitrinite. The photoacoustic measurements reflect the chemical composition and molecular structure of the individual coal macerals.     

Electrochemical oxidation of coals: Voltammetry and mass spectrometry

The anodic oxidation of sulphuric acid slurries of lignite, bituminous, and anthracite coals; a high-yield extract of coal; and carbon black, has been investigated voltammetrically and with simultaneous m.s. monitoring of evolved gases. The previously reported evolution of carbon dioxide at very low voltages was shown to be chemically released from minerals. The low rank coals and the asphaltite did show considerable electrochemical activity near to 1.0–1.2 V, mainly from the conversion of leached ferrous ion to the ferric form. Further activity near 1.4–1.5 V arose from the oxidation to CO₂ of leached organic matter. For well-washed low rank coals, the coal extract and the anthracite, CO₂ release was only observed at high (>2.8V) anode voltages, with simultaneous release of oxygen. Electrochemical gasification of coal via anodic oxidation of macromolecules at low voltages did not occur.     

Thermoplastic properties of coal at elevated pressures: 1. Evaluation of a high-pressure microdilatometer

Thermoplastic behaviour of a Pittsburgh seam hvA coal (PSOC1099) was characterized by the use of a high-pressure microdilatometer. Phenomena such as softening, swelling, final resolidification, and the temperatures at which they occur were measured as functions of heating rate (25 ° and 65 °C min^?1), particle size (= 75 μm and 250 × 425 μm), gaseous atmosphere (N₂, H₂, $\text{CO}\text{H}{}_2$) and applied gas pressure (atmospheric to 2.8 M Pa). The results obtained illustrate several important aspects of thermoplastic properties of this coal under the conditions utilized. It is observed that pressure alone can play a major role in determining its overall thermoplastic behaviour. Compared to that at atmospheric pressure, swelling is significantly reduced at 2.8 MPa of pressure for any given heating rate or particle size. In these experiments, the chemical composition of the gaseous atmospheres ($\text{CO}\text{H}{}_2$, H₂ and N₂) does not appear to alter significantly the plastic phenomena at any given pressure. Increasing the heating rate or decreasing the particle size results in increased swelling at all applied pressures and atmospheres.     

Gasification of coals treated with non-aqueous solvents. 6. Catalytic steam gasification at atmospheric pressure

Nickel-catalysed steam gasification was examined for two Japanese and three German coals which had been pretreated with liquid ammonia. Reaction temperatures range from 923 to 1123 K. The greatest enhancement in reactivity by ammonia treatment and 1 wt % nickel loading was observed for Leopold coal. With this treatment, the temperature could be lowered by about 55 K to achieve the same conversion level as the original coal. The apparent activation energy decreased from 220 to 140 J/mol. The crucible swelling number decreased from $\text{1}\text{1}\text{2}$to 0. The surface of the char after gasification was examined by a scanning electron microscope. The role of the catalyst and the interaction of nickel with sulphur are discussed.     

Influence of coal preoxidation and the relation between char structure and gasification potential

A study was carried out to ascertain the effects of coal preoxidation and carbonization conditions on the structure and relative gasification potential of a series of bituminous coal chars. Chars were prepared from two freshly mined bituminous coals and preoxidized samples derived from them. Carbonization conditions included a wide range of heating rate (0.2–10000K s^?1), temperature (1073–1273 K) and time (0.25–3600 s). Char properties were characterized in terms of analysis of char morphology, surface area, elemental composition, and gasification reactivity in air. Over the range of conditions used, preoxidation substantially reduced coal fluid behaviour and influenced macroscopic char properties (char morphology). Following slow heating (0.2 K s^?1), preoxidized coals yielded chars having higher total surface areas and higher reactivities toward gasification in air than did similar chars prepared from fresh coal. Following rapid heating (10000 K s^?1) and short residence times (0.25 s), chars prepared from preoxidized and fresh coals exhibited similar microstructural and chemical properties (surface area, $\text{C}\text{H}$ ratios, gasification rates). Carbonization time and temperature were found to be the critical parameters influencing char structure and gasification potential.     

High-temperature 1H n.m.r. study of oxidized coal

Two coking coals, a caking and a non-caking coal are examined in a Bruker pulsed ¹H n.m.r. spectrometer in the temperature range 293–730 K. One coking and the caking coal are oxidized in air at 383 K for 13 days. Temperatures of signal appearance and loss are noted as well as the temperatures of minimum signal half-peak width ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$). There occurs no change in the above three temperatures with oxidation of the coals. The variation of ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) with temperature of the coal is also measured. Changes in ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) are more pronounced for the caking coal. The softening and solidification temperatures are below and above, respectively, those reported using the Gieseler method. Values of ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) increase beyond the minimum value as the fluidity continues to increase. This may be caused by an increase in average molecular weight of constituent molecules and/or an increasing concentration of free radicals in the fluid phase. This experimental approach may afford a new method to characterize coals which are to be used in liquefaction processes.     

Chemical beneficiation of coal with aqueous hydrogen peroxide/sulphuric acid solutions

The removal of sulphur and ash from coal treated with aqueous hydrogen peroxide/sulphuric acid solutions has been studied at ambient temperature, under a variety of experimental conditions. Almost complete elimination of the sulphate and the pyritic sulphur was observed in most cases, as well as substantial reduction in the ash content. The other components of the organic coal matrix were not affected to a significant extent, indicating high selectivity of the $\text{H}{}_2\text{O}{}_2\text{H}{}_2\text{SO4}$ system towards sulphur oxidation. An optimal H₂SO₄ concentration was established, above which the acid was found to have an adverse effect on the oxidation of pyrite by hydrogen peroxide.     

Internal rearrangement of hydrogen during heating of coals with phenol

Heating either Bruceton or Wyodak coal with phenol results in the thermal depolymerization of the coal yielding pyridine-soluble products and an insoluble residue. The depolymerization is accompanied by extensive rearrangements of hydrogen within the coals producing a soluble material enriched in hydrogen and a residue which is hydrogen poor. The hydrogen shuttle in Wyodak coal has a different temperature dependence than does the depolymerization, being favoured at higher temperatures. The $\text{H}\text{C}$ ratio of the soluble products increased with increasing conversion. Relatively small amounts (ca. 5%) of the products at high conversion are derived from phenol.