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.     

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.     

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.     

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.     

Mechanism on the contribution of coal/char fragmentation to fly ash formation during pulverized coal combustion

In this paper, the correlations between coal/char fragmentation and fly ash formation during pulverized coal combustion are investigated. We observed an explosion-like fragmentation of Zhundong coal in the early devolatilization stage by means of high-speed photography in the Hencken flat-flame burner. While high ash-fusion (HAF) bituminous and coal-derived char samples only undergo gentle perimeter fragmentation in the char burning stage. Simultaneously, combustion experiments of two kinds of coals were conducted in a 25?kW down-fired combustor. The particle size distributions (PSDs) of both fine particulates (PM_1-10) and bulk fly ash (PM₁₀₊) were measured by Electrical Low Pressure Impactor (ELPI) and Malvern Mastersizer 2000, respectively. The results show that the mass PSD of residual fly ash (PM₁₊) from Zhundong coal exhibits a bi-modal shape with two peaks located at 14?µm and 102?µm, whereas that from HAF coal only possesses a single peak at 74?µm. A hybrid model accounting for multiple-route ash formation processes is developed to predict the PSD of fly ash during coal combustion. By incorporating coal/char fragmentation sub-models, the simulation can quantitatively reproduce the measured PM₁₊ PSDs for different kinds of coals. The sensitivity analysis further reveals that the bi-modal mass distribution of PM₁₊ intrinsically results from the coal fragmentation during devolatilization.     

Realization of oxyfuel combustion for near zero emission power generation

Oxyfuel combustion is one of the promising carbon capture and storage (CCS) technologies for coal-fired boilers. In oxyfuel combustion, combustion gas is oxygen and recirculating flue gas (FGR) and main component of combustion gas is O₂, CO₂ and H₂O rather than O₂, N₂ in air combustion. Fundamental researches showed that flame temperature and flame propagation velocity of pulverized cloud in oxyfuel combustion are lower than that in air with the same O₂ concentration due to higher heat capacity of CO₂. IHI pilot combustion test showed that stable burner combustion was obtained over 30% O₂ in secondary combustion gas and the same furnace heat transfer as that of air firing at 27% O₂ in overall combustion gas. Compared to emissions in air combustion, NOx emission per unit combustion energy decreased to 1/3 due to reducing NOx in the FGR, and SO_x emission was 30% lower. However SO_x concentration in the furnace for the oxyfuel mode was three to four times greater than for the air mode due to lower flow rate of exhaust gas. The higher SO₃ concentration results that the sulphuric acid dew point increases 15–20 °C compared to the air combustion. These results confirmed the oxyfuel pulverized coal combustion is reliable and promising technology for coal firing power plant for CCS.In 2008, based on R&D and a feasibility study of commercial plants, the Callide Oxyfuel Project was started in order to demonstrate entire oxyfuel CCS power plant system for the first time in the world. The general scope and progress of the project are introduced here. Finally, challenges for present and next generation oxyfuel combustion power plant technologies are addressed.     

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.     

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.     

Interactions of potassium vapor with reactor tubes made of different materials and their impacts on particulate matter emission during pulverized biomass combustion

During the combustion of biomass in drop-tube furnace (DTF) systems, the released alkali metal (e.g., potassium, K) inevitably reacts with reactor tube at high temperatures, affecting the experimental results on the emission of particulate matter with aerodynamic diameters of <10 μm (PM₁₀). This study reports the interactions between K vapor and tube reactors made of silicon carbide, corundum, and mullite and their impacts on PM₁₀ emission. Demineralized wood samples loaded with potassium chloride (KCl) or ion-exchanged K respectively were combusted in a DTF at 1300 °C under air or oxy-fuel atmosphere. Another series of experiments was conducted to collect and analyze the PM₁₀ from the combustion of KCl-loaded wood, K-exchanged wood, and two typical biomass samples (cotton stalk and wheat straw) in the three reactor tubes under air atmosphere. Experimental results show that 4.1‒72.5% of K is retained in the three tubes when burning the KCl-loaded wood in air, and the combustion in oxy-fuel atmosphere slightly increases the K retention. For K-exchanged wood combustion in air, only 3.7‒23.6% of K is released from the reactor tubes. In all conditions, the reactivity of the reactor tubes with K vapor follows a sequence of mullite > corundum > silicon carbide. The retained K is unstable, 49.0‒64.8% of which can be re-released during polyvinyl chloride combustion. In addition, the results demonstrate that, compared with silicon carbide tube, the use of corundum and mullite tubes leads to a 16.2‒54.3% decrease in PM₁ yields and a significant drop in fine mode peaks in PM₁₀ during the combustion of biomass samples in air, while the PM_1–10 yields and the coarse mode peaks remain largely unchanged. These are attributed to the enhanced retentions of alkali metals in corundum and mullite tubes, which reduce the yields of Na, K, and Cl in PM₁₀, but has negligible effect on those of refractory elements such as Mg and Ca.     

In-situ gasification chemical looping combustion of plastic waste in a semi-continuously operated fluidized bed reactor

Conventional air incineration of plastic waste has been considered as one of important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) through de novo synthesis and precursor conversion. Chemical looping combustion (CLC) is an attractive technology for the conversion of plastic wastes to energy with the potential to drastically suppress the formation of PCDD/Fs. In this paper, the iG-CLC (in-situ gasification CLC) experiments of plastic waste were implemented in a semi-continuously operated fluidized bed reactor, which actually simulates the fuel reactor of a continuously-operated interconnected fluidized bed reactor. A kind of low-cost material, natural iron ore without/with 5 wt% CaO adsorbent through the ultrasonic impregnation method, was used as oxygen carrier (OC). Firstly, some key performances of the reactor system, such as the relevance of the bed inventory to the flow rate of fluidizing agent as well as the relationship between the feeding rate and overflow rate of OC, were calibrated. Then, 90 min of single experiment was conducted for each experimental case and an accumulative operation of more than 10 h was attained. Typically, the combustion efficiency can reach at about 98%, and both the carbon conversion and CO₂ yield can approach to 95% at 900 °C and input thermal power of 150 W with a mixture of 5 vol% H₂O and 95 vol% N₂ as the fluidizing agent (U_FR/U_mf = 3). Moreover, the results obtained in the semi-continuously operated fluidized bed reactor demonstrated that CaO decoration to iron ore is conductive to suppressing the formation of chlorobenzene (as a toxic matter and precursor/intermediate of PCDD/Fs) and does not obviously deteriorate the OC performance.     

Kinetic analysis of n-decane–hydrogen blend combustion in premixed and non-premixed supersonic flows

Numerical analysis of ignition and combustion of an n-decane–hydrogen fuel blend in a premixed supersonic flow and in a model scramjet duct is performed using a reduced reaction mechanism built especially to describe the oxidation of blended n-C₁₀H₂₂–H₂ fuel in air at the temperature T₀ > 900–1000 K in the pressure range P₀ = 0.1–13 atm. The developed kinetic mechanism involves the principal reactions responsible for chain mechanism development both for n-decane and for hydrogen oxidation. It has been shown that using blended n-C₁₀H₂₂–H₂ fuel makes it possible to enhance the ignition and combustion both in premixed and in non-premixed supersonic fuel–air flows compared to burning pure hydrogen–air and n-decane–air mixtures. This allows high combustion completeness in the scramjet duct at the distance of ～1 m even at extremely low air temperature T₀ = 1000 K and pressure P₀ = 0.3 atm. This is due to the interaction of kinetics of the formation of highly reactive atoms and radicals, carriers of chain mechanism, in H₂–air and n-C₁₀H₂₂–air mixtures.     

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.     

In situ upgrading of bio-oil via CaO catalyst derived from organic precursors

The fast pyrolysis of biomass with catalysts is a promising route for producing upgraded bio-oil as an alternative energy source. A CaO catalyst prepared from organic calcium compounds (Org-CaO) was first used to upgrade the pyrolysis oil of Jatropha curcas seeds in situ. Calcium d-gluconate monohydrate, calcium citrate tetrahydrate, and calcium acetate hydrate were employed as the organic precursors in this work. The results showed that Org-CaO exhibited better deoxygenation ability to produce more hydrocarbons than conventional CaO derived from Ca(OH)₂ (CHCaO). Acids accounted for 83% of the oxygenated compounds in the raw bio-oil and were almost completely removed via CaO. For bio-oil catalyzed by Org-CaO, the fraction of esters in the oxygenated compounds was only ～9%, which was 20% less than that in CHCaO bio-oil. The relative content of ketones and alcohols in Org-CaO bio-oil increased by 16% versus that in CHCaO bio-oil. Org-CaO exhibited a remarkably larger pore size and much smaller particle sizes. Thus, Org-CaO entered into the fuel through the pore channels, and this promoted the formation of chemical crosslinking points between CaO and oxygenated groups. In addition, the basicity and the amount of basic sites for Org-CaO increased versus CHCaO. Thus, the adsorption forms of oxygen-containing groups in the bio-oil on the basic sites of CaO changed: the carboxyl groups were removed from the acids and were absorbed in a stable form of unidentate carbonate on oxygen vacancies (O^2?). The stable form was bidentate carbonate on Ca²⁺–O^2?. In addition, oxygen vacancies on Org-CaO extracted more hydroxyl groups from the acids, resulting in dehydroxylation of acids to form ketones and alcohols.     

Synthesis and performance of Sm0.9Sr0.1Cr0.5Fe0.5O3 as anode material for SOFCs running on H2S-containing fuel

Sm_0.9Sr_0.1Cr_0.5Fe_0.5O₃ (SSCF) was successfully synthesized by gel combustion method. The structure and physicochemical properties of SSCF were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR). The results showed that SSCF had orthorhombic perovskite-type structure and a homogeneous distribution of pores and particles with grain size in the range 200–300 nm. Meanwhile, SSCF exhibited good chemical compatibility with electrolyte Ce_0.8Sm_0.2O_1.9 (SDC), and no additional diffraction peaks associated with impurities were observed after exposure to 10 %?v/v H₂/N₂ and 1 %?v/v H₂S/N₂. The conductivities of SSCF were evaluated with DC four-probe method in various atmospheres at 400–800 °C. The highest conductivities of SSCF were 0.56, 0.26 and 0.12 S?cm^?1 in air, 10 %?v/v H₂/N₂ and 1 %?v/v H₂S/N₂, respectively. The electrochemical properties were measured for the cell with configuration of SSCF-SDC/SDC/Ag at different temperatures. Electrochemical impedance spectroscopy (EIS) revealed that with the increase in temperature, the ohmic and total interfacial resistances of the cell decreased and the ohmic resistance gradually became the main factor affecting the performance of the cell.     

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.     

Soot particle size distribution measurements in a turbulent ethylene swirl flame

There is a need to better understand particle size distributions (PSDs) from turbulent flames from a theoretical, practical and even regulatory perspective. Experiments were conducted on a sooting turbulent non-premixed swirled ethylene flame with secondary (dilution) air injection to investigate exhaust and in-burner PSDs measured with a Scanning Mobility Particle Sizer (SMPS) and soot volume fractions (f_v) using extinction measurements. The focus was to understand the effect of systematically changing the amount and location of dilution air injection on the PSDs and f_v inside the burner and at the exhaust. The PSDs were also compared with planar Laser Induced Incandescence (LII) calibrated against the average f_v. LII provides some supplemental information on the relative soot amounts and spatial distribution among the various flow conditions that helps interpret the results. For the flame with no air dilution, f_v drops gradually along the centreline of the burner towards the exhaust and the PSD shows a shift from larger particles to smaller. However, with dilution air f_v reduces sharply where the dilution jets meet the burner axis. Downstream of the dilution jets f_v reduces gradually and the PSDs remain unchanged until the exhaust. At the exhaust, the flame with no air dilution shows significantly more particles with an f_v one to two orders of magnitude greater compared to the Cases with dilution. This dataset provides insights into soot spatial and particle size distributions within turbulent flames of relevance to gas turbine combustion with differing dilution parameters and the effect dilution has on the particle size. Additionally, this work measures f_v using both ex situ and in situ techniques, and highlights the difficulties associated with comparing results across the two. The results are useful for validating advanced models for turbulent combustion.     

Photo-physical properties of anisole: temperature, pressure, and bath gas composition dependence of fluorescence spectra and lifetimes

Anisole is a promising candidate for use as fluorescent tracer for gas-phase imaging diagnostics. Its high-fluorescence quantum yield (FQY) and its large Stokes shift lead to improved signal intensity (up to 100 times stronger) compared with the often used toluene. Fluorescence spectra and effective fluorescence lifetimes of gaseous anisole were investigated after picosecond laser excitation at 266 nm as a function of temperature (296–977 K) and bath gas composition (varying amounts of N₂ and O₂) at total pressures in the range of 1–10 bar to provide spectroscopic data and FQY for applications, e.g., in in-cylinder measurements in internal combustion engines. Fluorescence spectra of anisole extend from roughly 270–360 nm with a peak close to 290 nm at 296 K. The spectra show a red-shift with increasing temperature (0.03 nm/K) and O₂ partial pressure (5 nm from N₂ to air). In the investigated temperature range and in pure N₂ at 1 bar total pressure the effective fluorescence lifetime drops with increasing temperature from 13.3 ± 0.5 to 0.05 ± 0.01 ns. Increasing the total pressure of N₂ leads to a small decrease of the lifetime at temperatures above 400 K (e.g., at 525 K from 4.2 ± 0.2 ns at 1 bar to 2.7 ± 0.2 ns at 10 bar). At constant temperature and in the presence of O₂ the lifetimes decrease significantly (e.g., at 296 K from 13.3 ± 0.5 ns in N₂ to 0.40 ± 0.02 ns in air), with this trend diminishing with increasing temperature (e.g., at 675 K from 1.02 ± 0.08 ns in N₂ to 0.25 ± 0.05 ns in air). A phenomenological model that predicts fluorescence lifetimes, i.e., relative quantum yields as a function of temperature, pressure, and O₂ concentration is presented. The photophysics of anisole is discussed in comparison with other aromatics.     

PVA-assisted synthesis and characterization of nano-crystalline La3+ and Mg2+ co-doped CeO2 electrolyte for intermediate-temperature solid oxide fuel cells

A series of nano-crystalline ceria-based solid solution electrolyte, Ce_0.8La_0.2?x Mg_xO_2?δ (x?=?0.0, 0.05, 0.10, 0.15, and 0.2), were synthesized via the polyvinyl alcohol (PVA) assisted combustion method, and then characterized to the crystalline structure, powder morphology, sintering micro-structure, and electrical properties. Present study showed that Ce_0.8La_0.2?x Mg _x O_2?δ was exceedingly stable as a cubic phase in all temperature range and exhibited fine crystals ranging from 15 to 20 nm. After sintering at 1,400 °C, the as-prepared pellets exhibited a dense micro-structure with 96 % of theoretical density. The electrical conductivity was studied using AC impedance spectroscopy and it was observed that the composition Ce_0.8La_0.1?Mg_0.1O_2?δ showed higher electrical conductivity of 0.020 S?cm^?1 at 700 °C. The thermal expansion was measured using dilatometer technique in the temperature range 30–1,000 °C. The average thermal expansion coefficient of Ce_0.8La_0.1?Mg_0.1O_2?δ was 12.37?×?10^?6 K^?1, which was higher than that of the commonly used SOFC electrolyte YSZ (~10.8?×?10^?6 K^?1).     

Influence of nitrogen in aluminum droplet combustion

The influence of nitrogen on the aluminum droplet combustion under forced convection conditions has been studied. An aerodynamic levitation technique of millimetric size liquid droplets heated with a CO₂ laser has been adopted to characterize the combustion of aluminum droplets and, in particular, to observe the surface phenomena. The determination of the burning rate and of the droplet temperature in several atmospheres (H₂O/O₂, H₂O/Ar, H₂O/N₂, and air) has shown that they depend only on the nature and concentration of the oxidizers (O₂ and H₂O); a comparison of experiments in nitrogen and in argon containing mixtures demonstrated that N₂ did not influence the gas phase combustion. However, for nitrogen containing atmospheres we observed the formation of solid aluminum nitride (AlN) at the droplet surface after a latency time depending on the nitrogen pressure. AlN first interacts with the oxide cap producing an aluminum oxynitride, then completely covers the droplet, and finally prevents combustion. The existence of a latency time varying with the nitrogen pressure suggests that the AlN formation is controlled by heterogeneous kinetics. The phenomenon of oxide cap regression during combustion was also observed in all gases, and it is attributed to a chemical decomposition process of alumina by aluminum forming gaseous Al_xO_y species. Therefore, nitrogen effects are significant at the droplet surface rather than in the gas phase, and it is suggested that N₂ is probably one of the main species causing the manifestation of unsteady processes during aluminum droplet burning.     

High-temperature transformation of pyrite in CO2: Effects of residence time and the presence of O2

To understand the behavior of pyrite (a key slag-inducing coal mineral) in oxyfuel combustion (O₂/CO₂ combustion), our previous work firstly investigated the effects of pure CO₂ on fixed bed reactors and at low temperatures (<1273 K) and long residence time (order of minutes). As a consecutive contribution, this work explores pyrite transformation in CO₂ with the presence of O₂ on a drop tube furnace (DTF) and at a high temperature of 1573 K. These conditions are more relevant to practical oxyfuel combustion. Pulverized pyrite samples of sizes between 63 and 75 µm were tested in CO₂ with varying O₂ from 0 to 3%, mimicking the conditions near the boiler burners. The changes of pyrite transformation with residence time were investigated by examining the intermediate products, collected by a high-temperature sampling probe. For a clear clarification of the effects of CO₂, tests were also carried out in O₂/N₂ for comparison. The solid products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS). The gas products were analyzed online by a gas analyzer. Results showed that, in the absence of O₂, CO₂ chemically accelerated pyrite decomposition and oxidation when compared with N₂. This finding was consistent with that in previous work performed on fixed-bed reactors. In the presence of the same O₂ concentration, the positive roles of CO₂ persisted, enhancing the formation of magnetite (Fe₃O₄) and SO₂. In either O₂/CO₂ or O₂/N₂, increasing O₂ concentration also favored the formation of magnetite and SO₂. Significant changes of SO₂ and S in pyrrhotite (FeS_x) were observed between 0.5–0.7 s, and longer residence time did not seem to have significant effects. However, the amount of magnetite formed increased with increasing residence time. The obtained knowledge is new and very useful to further understanding of pyrite behavior in real oxyfuel combustion systems.