Effect of water vapour on particulate matter emission during oxyfuel combustion of char and in situ volatiles generated from rapid pyrolysis of chromated-copper-arsenate-treated wood

This paper reports the effect of water vapour on particulate matter (PM) during the separate combustion of in situ volatiles and char generated from chromated-copper-arsenate-treated (CCAT) wood at 1300 °C. Combustion of in situ volatiles produces only PM with aerodynamic diameter?<1?µm (i.e., PM₁), dominantly PM with aerodynamic diameter?<0.1?µm (i.e., PM_0.1). Water vapour could significantly enhance the nucleation, coagulation and condensation of fine particles and reduce the capture of Na and K by the alumina reactor tube via reduced formation of alkali aluminates, leading to increases in both yield and modal diameter of PM_0.1. Water vapour could also enhance char fragmentation hence increase the yield of PM with aerodynamic diameter between 1 and 10?µm (i.e., PM_1–10) during char combustion. For trace elements, during in situ volatiles combustion, volatile elements (As, Cr, Ni, Cu and Pb) are only presented in PM₁ and water vapour alters the particle size distributions (PSDs) but has little effect on the yields of these trace elements. During char combustion, As, Cr, Cu and Ni are present in both PM₁ and PM_1–10 while the non-volatile Mn and Ti are only present in PM_1–10. Increasing water vapour content increases the yields of As, Cr, Cu, Ni, Mn and Ti in PM_1-10 due to enhanced char fragmentation. During char combustion, water vapour also originates less oxidising conditions locally for enhancing As release, promotes the generation of gaseous chromium oxyhydroxides and inhabits the production of NiCl₂ (g), leading to increased yields of As and Cr and decreased yield of Ni in PM_0.1.     

Fragmentation of pulverized coal in a laminar drop tube reactor: Experiments and model

Fragmentation during pulverized coal particles conversion shifts the particle size distribution of the fuel towards smaller particle sizes, affecting both conversion rates and heat release. After pyrolysis of a high volatiles Colombian coal in CO₂ atmosphere in a drop tube reactor at 1573?K, solid carbonaceous particles of different size, from 100?µm of the particle feed down to the nanometric size, have been observed. A fragmentation model has been used to predict the fate of Colombian coal particles under the experimental conditions of the drop tube experiment and predict the particle size distribution (PSD). Model and experimental results are in very good agreement and indicate that in the DTR experiment the coal underwent almost complete pyrolysis and that fragmentation generated a 36?wt% population of particles with size close to 30?µm. The close match between the PSDs obtained from experiments and from the fragmentation model is an important novelty. It demonstrates that fragmentation occurs not only under fluidized bed conditions but also under the conditions of pulverized coal combustion. Experimentalists are warned against the fact that the fine particulate sampled at the outlet of laminar flow reactors and boilers is not always composed of soot only. Char fragments can be misidentified as soot. The implementation of fragmentation submodels in pulverized fuel combustion and gasification codes is highly recommended.     

PM10 formation during the combustion of N2-char and CO2-char of Chinese coals

The formation of PM₁₀ (particles less than or equal to 10 μm in aerodynamic diameter) during char combustion in both air-firing and oxy-firing was investigated. Three Chinese coals of different ranks (i.e., DT bituminous coal, CF lignite, and YQ anthracite) were devolatilized at 1300 °C in N₂ and CO₂ atmosphere, respectively, in a drop tube furnace (DTF). The resulting N₂-chars and CO₂-chars were burned at 1300 °C in both air-firing (O₂/N₂ = 21/79) and oxy-firing (O₂/CO₂ = 21/79). The effects of char properties and combustion conditions on PM₁₀ formation during char combustion were studied. It was found that the formation modes and particle size distribution of PM₁₀ from char combustion whether in air-firing or in oxy-firing were similar to those from pulverized coal combustion. The significant amounts of PM_0.5 (particles less than or equal to 0.5 μm in aerodynamic diameter) generated from combustion of various chars suggested that the mineral matter left in the chars after coal devolatilization still had great contributions to the formation of ultrafine particles even during the char combustion stage. The concentration of PM₁₀ from char combustion in oxy-firing was generally less than that in air-firing. The properties of the CO₂-chars were different from those of the N₂-chars, which was likely due to gasification reactions coal particles experienced during devolatilization in CO₂ atmosphere. Regardless of the combustion modes, PM₁₀ formation in combustion of N₂-char and CO₂-char from the same coal was found to be significantly dependent on char properties. The difference in the PM₁₀ formation behavior between the N₂-char and CO₂-char was coal-type dependent.     

An in-situ method for time-resolved sodium release behaviour during coal combustion and its application in industrial coal-fired boilers

To mitigate the slagging, fouling and high-temperature corrosion problems caused by alkali metals during coal combustion process, measurement of time-resolved alkali metals release is very important. The paper proposed an in-situ approach for measuring sodium (Na) release in coal combustion by Flame Emission Spectroscopy (FES). Through the analysis of spontaneous emission spectra and a calibration procedure, the concentration of gas phase Na, temperature and thermal radiation can be obtained. Firstly, experimental measurement of Zhundong coal particles burning in a flat flame burner was done. Two kinds of Zhundong coal with similar proximate and ultimate analyses, but different ash composition were used. The Na-release history measured by FES was compared with that by LIBS. Results showed that the Na-release at the devolatilization, char, and ash stages can be distinguished by FES. The higher Si/Al content in ash can suppress the Na-release at the ash stage. Moreover, FES method was extended to the measurement of Na-release in four industrial boiler furnaces of two Zhundong coal-fired power plants. Results showed the Na-release measured by FES can reflect the change of fuel and load, and both temperature and thermal radiation play key roles in Na-release in coal combustion.     

Investigating particle and volatile evolution during pulverized coal combustion using high-speed digital in-line holography

Devolatilization is an important process in pulverized coal combustion because it affects the ignition, volatile combustion, and subsequent char burning and ash formation. In this study, high-speed digital in-line holography is employed to visualize and quantify the particle and volatile evolution during pulverized coal combustion. China Shanxi bituminous coal particles sieved in the range of 105–154 µm are entrained into a flat flame burner through a central tube for the study. Time-resolved observations show the volatile ejection, accumulation, and detachment in the early stage of coal combustion. Three-dimensional imaging and automatic particle extraction algorithm allow for the size and velocity statistics of the particle and stringy volatile tail. The results demonstrate the smaller particle generation and coal particle swelling in the devolatilization. It is found that the coal particles and volatiles accelerate due to the thermal buoyancy and the volatiles move faster than the coal particles. On average, smaller particles move faster than the larger ones while some can move much slower possibly because of the fragmentation.     

Ash cenosphere fragmentation during pulverised pyrite combustion: Importance of cooling

This paper as the first time in the field reports the direct experimental evidence for demonstrating the important role of cooling in ash cenosphere fragmentation using a simple but unique combustion system. The combustion system used pulverised pyrite (38–45 µm) for combustion in drop-tube furnace under designed conditions (gas temperature: 1000 °C; residence time: 1.2 s), which produced dominantly ash cenosphere particles or fragments. The combustion products were quenched under various cooling conditions (represented by nominal cooling rates of 6400–11,800 °C/s) for sampling. The results show that increasing cooling rate from 6400 to 11,800 °C/s substantially intensifies ash cenosphere fragmentation. Such enhanced ash cenosphere fragmentation leads to a significant shift in the particle size distribution of ash collected in the cyclone (>10 µm) to much smaller sizes. It also produces considerably more particulate matter (PM) with aerodynamic sizes less than 10 µm (i.e., PM₁₀) that consists of dominantly PM with aerodynamic sizes between 1 and 10 µm (i.e., PM_1–10) and some PM with aerodynamic sizes less than 1 µm (i.e., PM₁). It is further noted that the PM₁ is mainly PM with aerodynamic sizes between 0.1 and 1 µm (i.e., PM_0.1–1) and to a considerably lesser extent PM with aerodynamic sizes less than 0.1 µm (i.e., PM_0.1). Chemical analyses further show that both ash and PM samples contain only Fe₂O₃, indicating that complete consumption of sulphur and full oxidation of iron have been achieved during pulverised pyrite combustion under the conditions.     

Effect of the torrefaction on the emission of PM10 from combustion of rice husk and its blends with a lignite

Torrefaction is a competitive biomass pretreatment technology. However, its impacts on particulate matter (PM) formation during biomass combustion and co-combustion with coal have little been investigated. This work provides new data on the formation of PM₁₀ (particulate matter with aerodynamic diameters less than or equal to 10 µm) from combustion of raw (RH), torrefied rice husk (TRH) and their blends with a lignite (SZ). All combustion experiments were carried out on a drop-tube furnace at 1300 °C and in air. The combustion-generated PM₁₀ was collected by a Dekati low pressure impactor and classified into 14 size fractions for further quantification and characterization. The results indicate that, compared with the RH, the TRH-derived PM₁₀₊ (particle size above 10?µm) contains more alkalis, leading to a decrease in the production of PM₁ (particle size below 1?µm). During co-combustion, fuel interactions promote the transformation of alkali chlorides to aluminosilicates. A considerable amount of water-soluble Ca and P in PM₁ transforms to PM_1–10 (particle size between 1–10?µm). As a result, the production of PM₁ (on an ash basis) decreases while that of PM_1–10 increases. Co-combustion of coal with torrefied rice husk is found to generate less PM₁ but more PM_1–10 than that with raw rice husk.     

Ash formation and deposition during combustion of pulverized torrefied wood and coal in a 100 kW downflow combustor

Torrefied wood originating from beetle-killed trees is an abundant biomass fuel that can be co-fired with coal for power generation. In this work, pulverized torrefied wood, a bituminous coal (Sufco coal) and their blended fuel with a mixing ratio of 50/50 wt.%, are burned in a 100-kW rated laboratory combustor under similar conditions. Ash aerosols in the flue gas and ash deposits on a temperature-controlled surface are sampled during combustion of the three fuels. Results show that ash formation and deposition for wood combustion are notably different from those for coal combustion, revealing different mechanisms. Compared to the coal, the low-ash torrefied wood produces low concentrations of fly ash in the flue gas but significantly increased yields (per input ash) of ash that has been vaporized. All the mineral elements including the semi- or non-volatile metals in the wood are found to be more readily partitioned into the PM₁₀ ash than those in the coal. The inside layer deposits sticking to the surface and the loosely bound outside deposits exposed to the gas both show a linear growth in weight during torrefied wood test. Unlike coal combustion, in which the concentration of (vaporized) ash PM₁ controls the inside deposition rate, wood combustion shows that the formation of porous bulky deposits by the condensed residual ash dominates the inside deposition process. Co-firing removes these differences between the wood and coal, making the blended fuel to have more similar fly ash characteristics and ash deposition behavior to those of the bituminous coal. In addition, results also show some beneficial effects of co-firing coal with torrefied wood, including reduction of the total deposition rate and the minimization of corrosive alkali species produced by wood.     

Measurements and modelling of oxy-fuel coal combustion

Oxy-fuel combustion is one of the most promising technologies to isolate efficiently and economically CO₂ emissions in coal combustion for the ready carbon sequestration. The high proportions of both H₂O and CO₂ in the furnace have complex impacts on flame characteristics (ignition, burnout, and heat transfer), pollutant emissions (NO_x, SO_x, and particulate matter), and operational concerns (ash deposition, fouling/slagging). In contrast to the existing literature, this review focuses on fundamental studies on both diagnostics and modelling aspects of bench- or lab-scale oxy-fuel combustion and, particularly, gives attention to the correlations among combustion characteristics, pollutant formation, and operational ash concerns. First, the influences of temperature and species concentrations (e.g., O₂, H₂O) on coal ignition, volatile combustion and char burning processes, for air- and oxy-firing, are comparatively evaluated and modelled, on the basis of data from optically-accessible set-ups including flat-flame burner, drop-tube furnace, and down-fired furnace. Then, the correlations of combustion-generated particulate/NO_x emissions with changes of combustion characteristics in both air and oxy-fuel firing modes are summarized. Additionally, ash deposition propensity, as well as its relation to the formation of fine particulates (i.e. PM_0.2, PM₁ and PM₁₀), for both modes are overviewed. Finally, future research topics are discussed. Fundamental oxy-fuel combustion research may provide an ideal alternative for validating CFD simulations toward industrial applications.     

Insight of arsenic transformation behavior during high-arsenic coal combustion

The release of arsenic vapors (As³⁺) during high-arsenic coal combustion not only raises serious environmental concerns, but also causes catalyst deactivation in selective catalytic reduction (SCR) systems. To illuminate the mechanisms involved in the transformation of arsenic vapors towards less troublesome arsenates (As⁵⁺) during coal combustion, the accessory minerals in the high-arsenic coal were identified and the association relationship of these compounds with arsenic in fly ash was estimated. The results showed that Si/Al were the main inorganic elements in high-arsenic coal while the content of Ca was quite low. Ca was mostly transformed into sulfates during coal combustion and the effect of Ca on the arsenic transformation was limited. Al/Fe played a more significant role in arsenic speciation transformation and arsenic in the fly ash was predominantly bound with Al/Fe-oxides as arsenates. It was further confirmed that Al in kaolin/metakaolin showed good capacity on arsenic capture. In addition, few arsenic vapors were captured through the physical adsorption mechanism and the large fraction of As³⁺ in some fine particles was mostly attributed to the chemical reactions between arsenic vapors and Al-compounds. Meanwhile, a certain amount of arsenic vapors were converted into As₂O₅(s) under the influence of SCR catalyst and then carried by flue gas to participate in fly ash. Besides, part of arsenic distributed in the fly ash was through the stabilization of ash matrix in high temperature conditions. The transformation of arsenic from vapors towards particulate arsenic favored arsenic emission control by particulate matter control devices.     

The progressive formation of submicron particulate matter in a quasi one-dimensional pulverized coal combustor

In this work, we aim to investigate the formation mechanisms of submicron particulate matter (PM₁) by observing progressive changes of collected samples at different combustion stages. A 25 kW quasi one-dimensional down-fired pulverized coal combustor was used, where PM₁ was collected from the furnace centerline through the desired sampling ports by using a nitrogen-aspirated, water-cooling isokinetic sampling probe followed a 13-stage electric low pressure impactor. First, the mass concentration particle-size-distributions (PSD) of PM₁ sampled at coal flame zone clearly exhibit two distinct modes separated by a fraction of 0.173–0.267 μm, ultrafine mode and intermediate mode. However, the ultrafine peak around 63 nm greatly decreases and becomes flat as coal combustion further progresses along axial length. Then, the contributions of either organically bounded minerals or inherent minerals to these two modes at different stages are analyzed. Finally, the evolution of sulfur-concentration PSD reveals the effects of pyrite decomposition and the sulfation reaction on PM₁ formation in the combustion system.     

Importance of flue gas cooling conditions in particulate matter formation during biomass combustion under conditions pertinent to pulverized fuel applications

Laboratory-scale experiments pertinent to pulverised fuel (PF) combustion are often carried out in drop-tube furnaces (DTFs) at air-fuel equivalence ratios and cooling rate for quenching flue gas that are much higher than those in PF boilers. This paper reports the effect of flue gas cooling conditions on the properties of PM with aerodynamic diameter of <10 µm (PM₁₀) from biomass combustion. This study considers four cooling rates (1000, 2000, 6000 and 20,000 °C/s) and two biomass feeding rates (0.05 and 0.25 g/min) that represents flue gases with significantly-different concentrations of inorganic vapours. The PSDs of PM₁₀ have a bimodal distribution with a fine mode within PM with aerodynamic diameter of <1 µm (PM₁) and a coarse mode within PM with aerodynamic diameter of 1–10 µm (PM_1–10). All experimental conditions produce PM₁₀ with similar PM₁ and PM_1–10 yields (～0.8 and ～1.6 mg/g_biomass, respectively) and similar coarse mode diameters (i.e. 6.863 µm). However, at a biomass feeding rate of 0.05 g/min, the fine mode diameter shifts from 0.022 to 0.077 µm when the cooling rate decreases from 20,000 to 1000 °C/s, indicating more profound heterogeneous condensation at a lower cooling rate. As the biomass feeding rate increases to 0.25 g/min, the fine mode diameter further shifts to 0.043 µm and at 20,000 °C/s but remained at 0.077 µm at 1000 °C/s though a clear shift of PSD to larger diameters is evident. These are attributed to enhanced heterogeneous condensation and coagulation of small particulates resulting from increased particle population density in hot flue gas. Chemical analyses show PM₁ contains dominantly volatile elements (i.e. Na, K and Cl) while PM_1–10 consists of mainly Ca. Similar trends are also observed for elemental PSDs and yields. It is also observed that slow cooling of hot flue gas leads to an increased yield of Cl in PM_1–10 due to enhanced chlorination of Ca species.     

Reduction effect of co-firing of torrefied straw and bituminous coal on PM1 emission under both air and oxyfuel atmosphere

Straw sample was torrefied at 260 °C and 300 °C in N₂, respectively, to prepare torrefied straw named as T-260 and T-300, and the reduction effect of co-firing straw or torrefied straw and steam coal on PM₁ is investigated. The combustion experiments were conducted in a high temperature drop tube furnace (DTF) at 1400 °C to collect the inorganic PM₁₀ for further analysis. Combustion atmosphere was air for all cases and 50% O₂/50% CO₂ (OXY50) for coal, T-260 and their blends of 1:1 and 4:1. The results show that all three biomass fuels show obvious emission reduction of PM with aerodynamic diameters of ≤?0.3?µm (PM_0.3) under both mix ratios. Reduction ratios of co-firing are overall higher at mix ratio of 1:1 than 4:1, and co-firing of T-260 or T-300 with coal shows higher reduction ratio than co-firing of straw. The higher ash content in torrefied straw leads to higher contents of alkali and alkaline earth metals (AAEM), which will further react with both Si and S during co-firing and coagulate into particles of larger sizes, leading to higher reduction ratios of PM_0.3 and unconspicuous reduction effects in PM_0.3–1 emitted from co-firing. During co-firing in oxyfuel atmosphere, a higher combustion temperature compared to air leads to an intensitive gasification, may resulting in effective and even higher reduction ratio in PM_0.3.     

Particle imaging of ignition and devolatilization of pulverized coal during oxy-fuel combustion

Oxy-fuel combustion of coal is a promising technology for cost-effective power production with carbon capture and sequestration that has ancillary benefits of emission reductions and lower flue gas cleanup costs. To fully understand the results of pilot-scale tests of oxy-fuel combustion and to accurately predict scale-up performance through CFD modeling, fundamental data are needed concerning coal and coal char combustion properties under these unconventional conditions. In the work reported here, the ignition and devolatilization characteristics of both a high-volatile bituminous coal and a Powder River Basin subbituminous coal were analyzed in detail through single-particle imaging at a gas temperature of 1700 K over a range of 12–36 vol % O₂ in both N₂ and CO₂ diluent gases. The bituminous coal images show large, hot soot cloud radiation whose size and shape vary with oxygen concentration and, to a lesser extent, with the use of N₂ versus CO₂ diluent gas. Subbituminous coal images show cooler, smaller emission signals during devolatilization that have the same characteristic size as the coal particles introduced into the flow (nominally 100 μm). The measurements also demonstrate that the use of CO₂ diluent retards the onset of ignition and increases the duration of devolatilization, once initiated. For a given diluent gas, a higher oxygen concentration yields shorter ignition delay and devolatilization times. The effect of CO₂ on coal particle ignition is explained by its higher molar specific heat and its tendency to reduce the local radical pool. The effect of O₂ on coal particle ignition results from its effect on the local mixture reactivity. CO₂ decreases the rate of devolatilization because of the lower mass diffusivity of volatiles in CO₂ mixtures, whereas higher O₂ concentrations increase the mass flux of oxygen to the volatiles flame and thereby increase the rate of devolatilization.     

Insight into the calcium carboxylate release behavior during Zhundong coal pyrolysis and combustion

In this paper, the dynamic behavior of calcium carboxylate release during Zhundong coal pyrolysis and combustion is studied via reactive molecular dynamics (ReaxFF MD) simulation. The molecular structure model of Zhundong coal is constructed based on the combination of the classic Hatcher coal model and experimental characterizations. Pyrolysis simulations on the coal model are performed at different temperatures ranging from 2000 K to 2800 K. The pyrolysis experiments are also carried out to validate the ReaxFF simulation. The results show that most of the calcium are released into the volatiles by the thermal decomposition of CM-Ca (coal/char matrix with calcium bonded) after releasing CO₂. The distributions of the calcium bonded to gas, tar and inorganics as well as the atomic calcium in the volatiles are quantitatively classified. The thermal cracking of tar fragments are significant at high temperatures leading to the conversion of calcium from tar into the organic gas. Furthermore, the nascent char model is constructed to study the release behavior of calcium in char combustion stage. The calcium is initially released in the form of oxidized calcium and atomic calcium. With increasing temperature, the oxidized calcium trends to convert to the organically bonded calcium. By using the Arrhenius expression, the kinetic parameters for the release of calcium into various species during pyrolysis and char combustion stages are quantitatively determined.     

An intrinsic kinetics model to predict complex ash effects (ash film,dilution, and vaporization) on pulverized coal char burnout in air (O2/N2) and oxy-fuel (O2/CO2) atmospheres

During coal combustion, char chemical reaction is the slowest step, particularly in the last burnout stage, where the char consists of small amounts of carbon in a predominant ash framework. Existing kinetics models tend to deviate from experimental measurements of late char burnout due to the incomplete treatment of ash effects. Ash can improve pore evolution through vaporization, hinder oxygen transport by forming an ash film, and reduce active carbon sites and available surface per unit volume by penetrating into the char matrix. In this work, a sophisticated kinetics model, focusing on these three ash evolution mechanisms (ash vaporization, ash film, and ash dilution) during pulverized coal (PC) char combustion, is developed by integrating them into a thorough mechanistic picture. Further, a detailed comparison of the three distinct ash effects on PC char conversion during air (O₂/N₂) and oxy-fuel (O₂/CO₂) combustion is performed. For the modeled coal, the mass of ash vaporization is approximate 3 orders less than the mass of ash remaining, which participates in ash dilution and ash film formation, both in O₂/N₂ and O₂/CO₂ atmospheres. The influence of these phenomena on burnout time follows the order: ash dilution > ash film > ash vaporization. The influence of ash vaporization on burnout time is minor, but through interactions with the ash dilution and ash film forming processes it can have an impact at high extents of burnout, particularly in O₂/CO₂ atmospheres. In O₂/N₂ atmospheres the residual ash predominately exists as an ash film, whereas it mainly exists as diluted ash in the char matrix in O₂/CO₂ atmospheres. The residual ash particle is encased by a thick film when the ash film forming fraction is high (low ash dilution fraction). These results provide in-depth insights into the conversion of PC char and further utilization of the residual ash.     

Mechanistic investigation into particulate matter formation during air and oxyfuel combustion of formulated water-soluble fractions of bio-oil

This paper reports a systematic study on the formation of particulate matter with diameter of <10 µm (i.e., PM₁₀) during the combustion of two formulated water-soluble fractions (FWSFs) of bio-oil in a drop-tube-furnace (DTF) at 1400 °C under air or oxyfuel (30%O₂/70%CO₂) conditions. FWSF-1 was an organic-free calcium chloride solution with a calcium concentration similar to that in the bio-oil. FWSF-2 was formulated from the compositions of major organics in bio-oil WSF, doped with calcium chloride at the same concentration. The results suggest that similar to bio-oil combustion, the FWSF combustion produces mainly particulate matter with diameter of between 0.1 and 10 µm (i.e., PM_0.1–10). Since there are no combustibles in the organic-free FWSF-1, the PM is produced via droplet evaporation followed by crystallization, fusion and further reactions to form CaO (in air or argon) or partially CaCO₃ (under oxyfuel condition). With the addition of organics, FWSF-2 combustion produces PM₁₀ shifting to smaller sizes due to extensive break up of droplets via microexplosion. Sprays with larger droplet size produce PM₁₀ with increased sizes. The results show that upon cooling CaO produced during combustion in air can react with HCl gas to form CaCl₂ in PM_0.1. The predicted PSDs of PM₁₀ based on the assumption that one droplet produces one PM particle is considerably larger than experimentally-measured PSDs of PM₁₀ during the combustion of FWSFs, confirming that breakup of spray droplets takes place and such breakup is extensive for FWSF-2 when organics are present in the fuel.     

Emissions of PM10 from the co-combustion of high-Ca pyrolyzed biochar and high-Si coal under air and oxyfuel atmosphere

The single or co-combustion experiments of high-Ca pyrolyzed biochar and high-Si coal were carried out on a drop tube furnace (DTF) at 1300 °C under air and oxyfuel (CO₂:O₂=50:50, oxy50) conditions. The produced PM₁₀ (of an aerodynamic diameter of 10 µm or less) was analyzed to investigate the interactions during co-combustion. Due to the characteristics of the selected samples (low S and Cl), the PM₁ emissions including PM_0.1 and PM_0.1–1 are very low during single combustion, except for the PM_0.1–1 emission during the combustion of biochar under oxy50 condition because of the massive partitioning of Mg, Ca and Fe. The interaction during co-combustion was observed to mainly occur in the generation of PM_1–10, and also slightly occur in the formation of PM_0.1–1 under oxy50 condition. The capture of Mg, Ca, and Fe from biochar by the Si-containing minerals in coal under the oxy50 condition results in a slight decrease in PM_0.1–1 during co-combustion. The higher the proportion of coal blended, the more obvious the reduction of elements. As for the formation of PM_1–10 during co-combustion, high-melting minerals of biochar would weaken the coalescence of minerals in coal to cause more PM₁₀, while the large mineral grains of coal would capture the minerals in biochar to generate more PM₁₀₊. Under the competition of the above two types of interactions, the experimental value of PM_1–10 yields was almost consistent with the theoretically calculated value, except for blended ratio of 80:20 (coal: biochar, air) or 50:50 (oxy50) with prior interaction predominating.     

Ultrafine ash aerosols from coal combustion: Characterization and health effects

Ultrafine coal fly-ash particles, defined here as those with diameters less than 0.5 μm, typically comprise less than 1% of the total fly-ash mass. These particles are formed primarily through ash vaporization, nucleation, and coagulation/condensation mechanisms, which lead to compositions notably different compared to other fine or coarse particle fractions formed by fragmentation. Whereas previous studies have focused on health effects of particulate matter with aerodynamic diameters less than 2.5 μm (PM_2.5) (including both vaporization and fragmentation modes), this paper reports results of interdisciplinary research focused on both characterization and health effects of primary ultrafine coal ash aerosols alone. Ultrafine, fine, and coarse ash particles were segregated and collected from a coal burned in a 20 kW laboratory combustor and two additional coals burned in an externally heated drop tube furnace. Extracted samples from both combustors were characterized by transmission electron microscopy (TEM), wavelength dispersive X-ray fluorescence (WD-XRF) spectroscopy, Mossbauer spectroscopy, and X-ray absorption fine structure (XAFS) spectroscopy. Pulmonary inflammation was characterized by albumin concentrations in mouse lung lavage fluid after instillation of collected particles in saline solutions and a single direct inhalation exposure. Results indicate that coal ultrafine ash sometimes, but not always, contains significant amounts of carbon, probably soot originating from coal tar volatiles, depending on coal type and combustion device. Surprisingly, XAFS results revealed the presence of chromium and thiophenic sulfur in the ultrafine ash particles. Although the single direct inhalation study failed to reveal significant health effects, the instillation results suggested potential lung injury, the severity of which could be correlated with the carbon (soot) content of the ultrafines. Further, this increased toxicity is consistent with theories in which the presence of carbon mediates transition metal (i.e., Fe) complexes, as revealed in this work by TEM and XAFS spectroscopy, promoting reactive oxygen species, oxidation–reduction cycling, and oxidative stress.     

Fundamental investigation into characteristics of particulate matter produced from rapid pyrolysis of biochar in a drop-tube furnace at 1300 °C

This paper reports the emission characteristics of leaf and wood biochar (LC500 and WC500) pyrolysis in a drop tube furnace at 1300 °C in argon atmosphere. The char yields at 1300 °C are ～ 65% and ～ 73% respectively for LC500 and WC500. Over 60% Mg, Ca, S, Al, Fe and Si are retained in char after pyrolysis at 1300 °C. The retentions of Na and K in the char from LC500 pyrolysis are lower than those in the char from WC500 pyrolysis due to release via enhanced chlorination as a result of much higher Cl content in LC500. Particulate matter (PM) with aerodynamic diameter of < 10 µm (i.e. PM₁₀) from LC500 and WC500 pyrolysis exhibits a bimodal distribution with a fine mode diameter of 0.011 µm and a coarse mode diameter of 4.087 µm. The PM₁₀ yield for LC500 pyrolysis is ～ 8.2 mg/g, higher than that of WC500 pyrolysis (～2.1 mg/g). Samples in PM_1-10 (i.e. PM with aerodynamic diameter 1 µm – 10 µm) are char fragments that have irregular shapes and similar molar ratio of (Na+K + 2Mg+2Ca)/(Cl+2S+3P) as the char collected in the cyclone. In PM₁ (i.e. PM with aerodynamic diameter < 1 µm), the main components in sample are inorganic species, and carbon only contributes to ～5% and ～8% the PM₁ produced from rapid pyrolysis of LC500 and WC500, respectively. Na, K and Cl are main inorganic species in PM₁, contributing ～ 98.8% and ～ 97.5% to all inorganic species. Na, K and Cl from rapid pyrolysis of biochar have a unimodal distribution with a mode diameter of 0.011 µm. In PM_1–10, Ca is the main inorganic specie, contributing to ～71.2% and ～65.3% to all inorganic species in PM_1–10 from pyrolysis of LC500 and WC500, respectively.