Coal-derived Particles Research Articles

High-Strength Formed Coke from Torrefied Biomass and Its Blend with Noncaking Coal

In continuation of our previous study on production of high-strength metallurgical coke from torrefied softwood (cedar), we studied coke production from a mixture of torrefied cedar (TC) and noncaking coal by pulverization to sizes <100 μm, mixing, binderless hot briquetting, and carbonization. These sequential processes produced coke with a tensile strength of 5–17 MPa, which was equivalent to or greater than that of conventional coke (5–6 MPa), from TC-coal mixtures over the entire ranges of TC mass fraction in briquette of 0–100%, torrefaction temperature of 250–300 °C, and choice of coal (sub-bituminous or medium-volatile bituminous coal). The mixing of TC and coal hindered densification of coke due to hindrance of shrinkage of more-shrinkable TC-derived particles during the carbonization under many of the conditions. Nevertheless, positive synergy occurred in the coke strength at TC mass fractions of over 50%, where coal-derived particles were dispersed in the matrix of TC-derived particles, bonded to them during the carbonization, and behaved as a reinforcement of the matrix. The bonding between TC-derived and coal-derived primary particles was revealed by scanning electron microscopy. Copulverization of mixed TC and coal to sizes <40 μm before the briquetting gave cokes having strengths as high as 23–28 MPa. The fine pulverization increased the frequencies of mutual bonding of TC-derived particles and coal-derived particles and bonding between TC-derived and coal-derived particles per coke volume. The strength of coke from the TC-coal mixture generally followed volume-based additivity of strengths of cokes from TC and coal. This was realized by mixing primary particles of TC and coal within ≈10 μm scale or even smaller.

The lack of microbial degradation of polycyclic aromatic hydrocarbons from coal-rich soils

Analytical techniques used to assess the environmental risk of contamination from polycyclic aromatic hydrocarbons (PAHs) typically consider only abiotic sample parameters. Supercritical fluid extraction and sorption enthalpy experiments previously suggested slow desorption rates for PAH compounds in two coal-contaminated floodplain soils. In this study, the actual PAH availability for aerobic soil microorganisms was tested in two series of soil-slurry experiments. The experimental conditions supported microbial degradation of phenanthrene if it was weakly sorbed onto silica gel. Native coals and coal-derived particles in two soils effectively acted as very strong sorbents and prevented microbial PAH degradation. The long history of PAH exposure and degree of coal contamination apparently had no influence on the capability of the microbial soil community to overcome constraints of PAH availability. Within the context of the experimental conditions and the compounds chosen, our results confirm that coal-bound PAHs are not bioavailable and hence of low environmental concern.

Aqueous accelerated solvent extraction of native polycyclic aromatic hydrocarbons (PAHs) from carbonaceous river floodplain soils

In this study, three river floodplain soils with different compositions of carbonaceous materials and a reference coal sample were extracted with water using the accelerated solvent extraction (ASE) method. The desorption enthalpy values for 2-ring PAHs were highest in the coal sample, with values in the soil samples decreasing with decrease in coal content. The values for the higher condensed PAHs showed that the highest desorption enthalpies were from the samples with the largest amount of coal-derived particles. Elevated desorption enthalpies indicated a strong bonding between PAHs and geosorbents. Moreover, with the application of ASE this study was able to conclude that the PAHs in the samples were preferentially adsorbed to carbonaceous materials with high surface areas.

Relationship between surface morphology and chemical composition of spheroidal carbonaceous particles within sediment core samples recovered from Osaka Bay, Japan

Spheroidal carbonaceous particles (SCPs) are produced by the high-temperature combustion of fossil fuels and are emitted to the atmosphere. Previous studies are divided regarding whether SCPs derived from the combustion of various fossil fuels can be identified based on their surface morphologies and chemical compositions. In this study, we examined the surface morphology and chemical composition of SCPs in sediment core samples collected from Osaka Bay, Japan, with the aim of evaluating the usefulness of SCPs morphology in identifying their origin. Scanning electron microscope (SEM) observations reveal three distinct surface morphologies: (1) smooth, (2) rough and irregular, and (3) convoluted and layered. According to a morphological classification scheme proposed previously, the former two morphologies correspond to coal-derived carbon particles, whereas the latter corresponds to oil-derived carbon particles. In terms of the chemical compositions of the particles with different morphologies, as analyzed by energy-dispersive spectroscopy, linear discriminant analysis reveals that the two fuel types can be distinguished. An overall success rate of >90% of reference of morphologically classified material correctly assigned to two groups that are chemically different each other, indicating a relationship between surface morphology and chemical composition. This result suggests that morphological characterization based on conventional SEM observations is useful in identifying the source fuel of SCPs.

PAH desorption from river floodplain soils using supercritical fluid extraction

Sequential supercritical fluid extraction (SFE) was performed in order to estimate desorption of PAHs from river floodplain soils which contain coal and coal-derived particles. Original soils, soils' light fractions (rho<2 g cm(-3)), and <63 microm fractions were studied for PAHs' desorption kinetics. Desorption data were successfully described using a two-site model. Desorption rate constants were one order of magnitude lower than those of "slow" and "very slow" desorption rates from other studies. This suggests very slow and extremely slow desorption. Estimated time scales releasing 99% of total extractable contaminants ranged from decades for 2-4-ring PAHs and hundreds of years for 5-6-ring PAHs. We demonstrate that, despite high soil PAH concentrations which are due to coal and coal-derived particles, the general environmental risk is reduced by the very slow and extremely slow desorption rates.

Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K(oc) values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.

Identification of carbonaceous geosorbents for PAHs by organic petrography in river floodplain soils

Organic petrographic analysis was applied to provide direct information on carbonaceous geosorbents for PAHs in river floodplain soils. The anthropogenic OM group (primarily coal and coal-derived particles) displayed large volume amounts for all the soil samples. Distinct PAH concentrations with similar PAH distribution patterns were determined in grain size and density fractions for each sample. Two-ring PAHs had stronger correlation to organic carbon (OC) than black carbon (BC) contents, while heavier PAHs showed correlation to BC, rather than OC. In this study, we combined grain size and density separation, PAH determinations, TOC and BC measurements, and organic petrographic identification, and concluded that two-ring PAHs in soils were associated to coal particles. Other heavier PAHs could be more controlled by black carbon (BC), which were mostly coal-derived particles from former coal mining and coal industrial activity.

Occurrence of coal and coal-derived particle-bound polycyclic aromatic hydrocarbons (PAHs) in a river floodplain soil

A PAH contaminated river floodplain soil was separated according to grain size and density. Coal and coal-derived particles from coal mining, coal industry and coal transportation activities were identified by organic petrographic analysis in our samples. Distinct concentrations of PAHs were found in different grain size and density fractions, however, similar distribution patterns of PAHs indicated similar sources. In addition, although light fractions had the mass fraction by weight of less than 5%, they contributed almost 75% of the total PAHs in the soil. PAH concentrations of all sub fractions showed positive correlation with their TOC contents. Altogether, coal and coal-derived particles that were abundant in light fractions could be the dominant geosorbents for PAHs in our samples.

Use of elemental size distributions in identifying particle formation modes

The chemical composition of particles generated during pulverized coal combustion is the consequence of their formation processes. This work aims to use the size resolved elemental composition of coal-derived particles to identify their formation modes. A size-classified bituminous coal is burnt in a laboratory drop tube furnace at 1150, 1250, and 1350 °C, respectively. The elemental composition of the size-segregated particles from coal combustion is analyzed and the total mass fraction size distributions of Si and Al are obtained. Three particle formation modes are observed in these distribution profiles. The coarse mode has the highest value of the total mass fraction of Si and Al while the ultrafine mode has the lowest one. The total mass fraction of Si and Al in these two modes is nearly independent of particle size. It is believed that the coarse mode is formed by the mineral coalescence mechanism and the ultrafine mode by the vaporization–condensation mechanism. The difference in the total mass fraction of Si and Al between the central mode and the other two indicates that the central mode is formed by different mechanisms. Based on the observation that the total mass fraction of Si and Al in this mode increases with increasing particle size, heterogeneous condensation of vaporized species on existing fine residual ash particles is proposed to account for the formation of these particles. The study of the elemental composition of the three modes represented in five categories verifies the proposed formation mechanisms for them to some extent.

Particle-scale understanding of the bioavailability of PAHs in sediment.

This study reports results of sediment bioslurry treatment and earthworm bioaccumulation for polycyclic aromatic hydrocarbon (PAH) contaminants found in sediment dredged from Milwaukee Harbor. A significant finding was that bioslurry treatment reduced PAHs on the sediment clay/silt fraction but not on the sediment coal-derived fraction and that PAH reduction in the clay/silt fraction correlated with substantial reduction in earthworm PAH bioaccumulation. These findings are used to infer PAH bioavailability from characterization of particle-scale PAH distribution, association, and binding among the principal particle fractions in the sediment. The results are consistent with work showing that the sediment comprised two principal particle classes for PAHs, coal-derived and clay/silt, each having much different PAH levels, release rates, and desorption activation energies. PAH sorption on coal-derived particles is associated with minimal biodegradation, slow release rates, and high desorption activation energies, while PAH sorption on clay/silt particles is associated with significant potential biodegradability, relatively fast release rates, and lower desorption activation energies. These characteristics are attributed to fundamental differences in the organic matter to which the PAHs are sorbed. Although the majority of the PAHs are found preferentially on coal-derived particles, the PAHs on the clay/silt sediment fraction are more mobile and available, and thus potentially of greater concern. This study demonstrates that a suite of tests comprising both bioassays and particle-scale investigations provide a basis to assess larger-scale phenomena of biotreatment of PAH-impacted sediments and bioavailability and potential toxicity of PAH contaminants in sediments. Improved understanding of contaminant bioavailability aids decision-making on the effectiveness of biotreatment of PAH-impacted sediments and the likelihood for possible reuse of dredged sediments as reclaimed soil or fill.

Particle-scale investigation of PAH desorption kinetics and thermodynamics from sediment.

Dredged sediment from Milwaukee Harbor showed two primary classes of particles in the <2 mm size range: a lighter-density coal- and wood-derived fraction with 62% of total PAHs and a heavier-density sand, silt, and clay fraction containing the remaining 38% of the PAHs. Room-temperature PAH desorption kinetic studies on separated sediment fractions revealed slow desorption rates for the coal-derived particles and fast desorption rates for the clay/silt particles. The effect of temperature on PAH release was measured by thermal program desorption mass spectrometry to investigate the desorption activation energies for PAHs on the different sediment particles. Three activated diffusion-based models and an activated first-order rate model were used to describe the thermal desorption of PAHs for four molecular weight classes. PAH binding with the coal-derived particles was associated with high activation energies, typically in the range of 115-139 kJ/mol. PAHs bound to the clay/silt material had much lower activation energy, i.e., in the range of 37-41 kJ/ mol for molecular weight 202. Among the desorption models tested, a spherical diffusion model with PAHs located like a rind on the outer 1-3 microm region best described the PAH thermal desorption response for coal-derived particles. This internal PAH distribution pattern on coalderived particles is based on prior direct measurement of PAH locations at the subparticle scale. These studies reveal that heterogeneous particle types in sediment exhibit much different amounts and binding of PAHs. PAHs associated with coal-derived particles aged over several decades in the field appear to be far from reaching an equilibrium sorption state due to the extremely slow diffusivities through the polymer-like coal matrix. These results provide an improved mechanistic perspective for the understanding of PAH mobility and bioavailability in sediments.

Impact of brown coal dust on the organic matter in particle-size fractions of a Mollisol

The influence of brown coal emissions from a briquette factory on the organic matter of a Mollisol has been investigated. Non-contaminated, heavily contaminated soils and airborne particles are compared by using chemical and spectroscopic methods ( 13C CPMAS-NMR, Py-GC-MS, 14C dating). Bulk soils as well as their particle-size fractions are investigated. Organic carbon content of the bulk contaminated soil (138.6 g C/kg) is higher by a factor of six than the non-contaminated soil. For particle-size fractions, the highest content of organic carbon is found in the fine sand fraction (347.2 g C/kg). Furthermore, organic matter of the contaminated site shows a trend for relatively higher abundance of aliphatic compounds in the fraction ranging from 6 to 2000 μm, whereas for particles < 6 μm no trend was observed. The A horizon of the contaminated soil is much older (15,750 yr BP0 than the non-contaminated soil, which indicates input of anthropogenic material. Py-GC-MS analyses show for the non-contaminated site a homologous series of mainly alkanes, low amounts of prist-1-ene and a high abundance of lignin- and carbohydrate-derived structures. In contrast, composition of the samples from the contaminated site are similar to a sample of brown coal analyzed and show a homologous series of n-alkane, alkene, α, ω-alkadiene triplets and a high relative abundance of prist-1-ene with few lignin derived compounds, except for the clay fraction. Reflected light microscopy shows large amounts of brown coal dust particles with typical maceral groups, huminite, liptinite, and inertinite, in the fine sand fraction from the contaminated soil. Additionally, minor amounts of thermally altered brown coal-derived particles, i.e. coke particles, are observed.

96/01874 Thermophoretic sampling of coal-derived soot particles during devolatilization

96/01874 Thermophoretic sampling of coal-derived soot particles during devolatilization