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.     

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.     

Re-examination of the phenolic hydroxyl contents of coals

In connection with studies of the dependence of liquefaction behaviour on coal characteristics, parameters were needed that might effectively characterize the organic chemical structures. Accordingly, the phenolic hydroxyl contents of 37 coals from three geological provinces of the USA have been determined, by acetylation with ¹⁴C-labelled acetic anhydride. The results, when expressed as fractions of the total organic matter in the coals, showed a good inverse correlation with the carbon contents (dmmf). However, application of a stepwise multiple regression analysis to the data developed a linear equation relating hydroxyl content to the vitrinite reflectance, calorific value and vitrinite content, the fraction of variance explained being 92%. When the hydroxyl contents were expressed in the alternative manner, as fractions of the total oxygen content, no correlation could be seen with carbon content. However, in the wide scatter of points on the graph, the data are seen to fall into three reasonably distinct populations such that at the same level of rank, hydroxyl contents typically decrease for coals from the three provinces in the order Interior > Eastern > Rocky Mountain, implying that coals from these areas differ in structure as a result of differing antecedents. Statistical analyses showed that $\text{OH}\text{O}$ has some significance in determining liquefaction behaviour, but it is not among the coal properties found most significant.     

DTGA combustion of coals in the Exxon coal library

Coal combustion experiments were carried out over the temperature range 25–900 °C using air at atmospheric pressure in a derivative thermogravimetric analysis system. Sixty-six coals high in vitrinite (> 80% mineral-matter-free basis) and low in inorganics (all but 12 samples < 10%) were examined as part of a coal characterization programme. The coals varied in rank from lignites (69% carbon on a dry, mineral-matter-free basis) to low-volatile bituminous (91% carbon). Combustion rates increased progressively with increasing temperature, passed through maxima and then declined. The rate data were fitted to an Arrhenius equation and plots showed four distinct regions of combustion. Apparent activation energies were calculated for each region and varied from ≈4 kJ mol^?1 in the high-temperature, diffusion-controlled region to 290 kJ mol^?1 in the chemical-reaction controlled, low-temperature region. The temperatures at which 50% of the sample had burned away ($\text{sol1}\text{2}\text{-}\text{life}$) were rectilinearly related to oxygen and carbon contents (correlation coefficient squared values of 0.88 and 0.86, respectively).     

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.     

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. Devolatilization of bituminous coals in a small fluidized-bed reactor

The devolatilization behaviour of ten bituminous coals was investigated under rapid heating conditions using a small-scale fluidized-bed pyrolyser. The pyrolyser operated continuously, coal particles being injected at a rate of 1–3 g h^?1 directly into a heated bed of sand fluidized by nitrogen. Yields of tar, C₁–C₃ hydrocarbon gases, and total volatile-matter and an agglomeration index are reported for all coals. Maximum tar yields were obtained at about 600 °C and were always substantially higher than those from the Gray-King assay. Total volatile-matter yields were also substantially higher than the proximate analysis values. The maximum tar yields appear to be directly proportional to the coal atomic $\text{H}\text{C}$ ratio. The elemental analysis of the tar is strongly dependent on pyrolysis temperature. The tar atomic $\text{H}\text{C}$ ratio is proportional to that of the parent coal. The effect on the devolatilization behaviour of two coals produced by changes in the pyrolyser atmosphere and the nature of the fluidized-bed material were also investigated. Substituting an atmosphere of hydrogen, helium, carbon dioxide or steam for nitrogen, has no effect on tar yield and, with one exception, little effect on the hydrocarbon gas yields. In the presence of hydrogen the yield of methane was increased at temperatures above 600 °C. Tar yields were significantly reduced on substituting petroleum coke for sand as the fluid-bed material. A fluidized bed of active char virtually eliminated the tar yield.     

Reduction of coal in hexamethylphosphoramide-Na-t-BuOH and the molecular weight distribution of pyridine-soluble material

Eight coals were reduced by hexamethylphosphoramide (HMPA)-Na-t-BuOH at room temperature and atmospheric pressure. More than 70 wt % of the coal is soluble in pyridine after this reduction. Coals having ≈88 wt% of carbon content show a maximum solubility in pyridine after reduction. The pyridine-soluble material has a higher $\text{H}\text{C}$ ratio after reduction. l.r. and n.m.r. spectra show that the reaction product is richer in aliphatic and olefinic structures and that the aromatic ring systems are extensively saturated. From g.p.c. separations and molecular weight measurements, it is found that the molecular weight distribution has a maximum at lower and higher molecular weight values. The average molecular weight of the reduced pyridine-soluble material decreases with increase in rank of the coal. Coking properties of these coals can be related to proportions of material in the two modes of distribution of molecular weight.     

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.     

Mineral matter as a measure of oxidation of a coking coal

The petrography, agglomerating characteristics, low-temperature ash (LTA) mineralogy and chemistry of ten consecutive channel samples from D seam, Natal Ridge, Crowsnest coalfield, British Columbia, were compared. It was found that there is a direct correlation between oxidation, as indicated by absence or limited caking character, and the presence of the mineral bassanite ($\text{CaS0}{}_4\text{·}\text{1}\text{2}\text{H}{}_2\text{O}$) in LTA. An attempt to estimate quantitatively the extent of oxidation by the anhydrite content in LTA samples further heated to 500 °C has resulted in the detection of partial oxidation of a coal sample having an FSI of $\text{6}\text{1}\text{2}$, reduced from a normal value of 8. The recognition and quantification of oxidation using epigenetic gypsum and its derivatives, however, probably only applies to the weakly pyritic, usually freshwater, coals typical of the Rocky Mountain coalfields of British Columbia and the Gondwana coalfields of the southern hemisphere.     

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.     

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.     

Characterization and catalytic activity of coal mineral matter: 1. Effect of hydrogen pretreatment and exposure to sulphur and nitrogen compounds

Low temperature ash (LTA) samples prepared from nine US coals were characterized by X-ray diffraction. X-ray fluorescence, and surface area analyses. The results showed that illite, kaolinite, quartz and pyrite are major components in LTAs and that $\text{S}\text{Fe}$ ratios of some LTAs decreased significantly after H₂ treatment implying the occurrence of a partial reduction of pyrite during this treatment. Surface areas of LTAs increased drastically on H₂ treatment but decreased after exposure to sulphur and nitrogen compounds in activity testing. Correlations for the surface areas of LTAs before and after H₂ treatment were found in terms of clay content and element concentrations.     

Pyrolysis studies of organic oxygenates. 2. Benzyl phenyl ether pyrolysis under batch autoclave conditions

Benzyl phenyl ether (BPE) is a reactive organic oxygenate which contains the ether functionality believed to be present in subbituminous and bituminous coals. With an $\text{H}\text{C}$ of 0.92 it has a $\text{hydrogen}\text{carbon}$ ratio similar to that found in bituminous coals. Benzyl phenyl ether reacts readily at 375 °C either in the presence or absence of added donor hydrogen sources. The major products are toluene and phenol. Other, heavier products are also produced in significant quantities. In general, as available donor hydrogen is reduced, the products tend to have higher molecular weights. Conventional pyrolysis products become lighter (more desirable) materials when the pyrolysis is carried out in the presence of added hydrogen.     

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.     

Interpretation of the chemical composition of bituminous coal macerals

Various methods of identifying and classifying macerals are evaluated on the basis of literature references and our own experimental results. Comparison of the diagrams $\text{H}\text{C}$ vs $\text{O}\text{C}$, atomic $\text{C}\text{H}$ ratio vs weight percentage of carbon, and atomic $\text{C}\text{H}$ ratio vs atomic percentage of carbon demonstrates the advantages of the characterization of maceral composition by means of the atomic carbon percentage, which is a function of the content of all five organogenic elements that enter into the composition of the combustible matter of caustobioliths. Illustration by means of maceral analyses from the same seam, of results from pyridine extraction, and of humic acid composition further confirms this view.     

Ruthenium tetroxide catalysed oxidation of Illinois No. 6 coal: The formation of volatile monocarboxylic acids

Ruthenium tetroxide selectively oxidizes activated aromatic compounds under mild conditions and has been used for the catalytic oxidation of several different coals. The quantities of the volatile monocarboxylic acids with 2–6 carbon atoms have been determined by an isotope dilution technique. The amount of ethanoic acid ranges from 1 to 3mol/100C and the quantities of propanoic acid, and butanoic acid exceed 0.1 mol/100C. Methylpropanoic, pentanoic, 2-methylbutanoic, 3-methylbutanoicand hexanoic acid are formed in lesser amounts. The outcome of the experiment depends upon whether or not the coal has been extracted prior to oxidation. The results for Illinois No. 6 coal expressed in moles of ethanoic acid produced/l00C illustrate this feature: raw whole coal, 1.9; coal extracted by the method of Hayatsu and co-workers, 1.0. Dehydrogenation with benzoquinone prior to oxidation increases the yield of ethanoic acid to $\text{sol1.5mol}\text{100C.}$ The amounts of ethanoic acid obtained from the other extracted coals are 1.0 for Texas lignite, 1.2 for Rawhide subbituminous, 3.4 for Pittsburgh No. 8, 3.3 for a higher ranking bituminous coal (PSOC 726) and 0.7 for an anthracite (PSOC872). The results obtained in this study are compared with related information concerning the distribution of alkyl groups within coal by other methods.     

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.     

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.