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.     

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.     

Effect of CO2 gasification reaction on oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, as is commonly employed, it is recognized that elevated CO₂ levels affect radiant transport, the heat capacity of the gas, and other gas transport properties. A topic of widespread speculation has concerned the effect of the CO₂ gasification reaction with coal char on the char burning rate. To give clarity to the likely impact of this reaction on the oxy-fuel combustion of pulverized coal char, the Surface Kinetics in Porous Particles (SKIPPY) code was employed for a range of potential CO₂ reaction rates for a high-volatile bituminous coal char particle (130 μm diameter) reacting in several O₂ concentration environments. The effects of boundary layer chemistry are also examined in this analysis. Under oxygen-enriched conditions, boundary layer reactions (converting CO to CO₂, with concomitant heat release) are shown to increase the char particle temperature and burning rate, while decreasing the O₂ concentration at the particle surface. The CO₂ gasification reaction acts to reduce the char particle temperature (because of the reaction endothermicity) and thereby reduces the rate of char oxidation. Interestingly, the presence of the CO₂ gasification reaction increases the char conversion rate for combustion at low O₂ concentrations, but decreases char conversion for combustion at high O₂ concentrations. These calculations give new insight into the complexity of the effects from the CO₂ gasification reaction and should help improve the understanding of experimentally measured oxy-fuel char combustion and burnout trends in the literature.     

The effect of bulk gas diffusivity on apparent pulverized coal char combustion kinetics

Apparent char kinetic rates are commonly used to predict pulverized coal char burning rates. These kinetic rates quantify the char burning rate based on the temperature of the particle and the oxygen concentration at the external particle surface, inherently neglecting the impact of variations in the internal diffusion rate and penetration of oxygen. To investigate the impact of bulk gas diffusivity on these phenomena during Zone II burning conditions, experimental measurements were performed of char particle combustion temperature and burnout for a subbituminous coal burning in an optical entrained flow reactor with helium and nitrogen diluents. The combination of much higher thermal conductivity and mass diffusivity in the helium environments resulted in cooler char combustion temperatures than in equivalent N₂ environments. Measured char burnout was similar in the two environments for a given bulk oxygen concentration but was approximately 60% higher in helium environments for a given char combustion temperature. To augment the experimental measurements, detailed particle simulations of the experimental conditions were conducted with the SKIPPY code. These simulations also showed a 60% higher burning rate in the helium environments for a given char particle combustion temperature. To differentiate the effect of enhanced diffusion through the external boundary layer from the effect of enhanced diffusion through the particle, additional SKIPPY simulations were conducted under selected conditions in N₂ and He environments for which the temperature and concentrations of reactants (oxygen and steam) were identical on the external char surface. Under these conditions, which yield matching apparent char burning rates, the computed char burning rate for He was 50% larger, demonstrating the potential for significant errors with the apparent kinetics approach. However, for specific application to oxy-fuel combustion in CO₂ environments, these results suggest the error to be as low as 3% when applying apparent char burning rates from nitrogen environments.     

Experimental study of influence of temperature on fuel-N conversion and recycle NO reduction in oxyfuel combustion

Coal combustion in O₂/CO₂ environment was examined with a bituminous coal in which the gas-phase and char combustion stages were considered separately. The effects of temperature (1000–1300 °C) and the excess oxygen ratio λ (0.6–1.4) on the conversion of volatile-N and char-N to NOx were studied. Also, the reduction of recycle NOx by fuel-N was investigated under various conditions. The results show that fuel-N conversion to NO in O₂/CO₂ is lower than that in O₂/N₂. In O₂/CO₂ atmosphere, the volatile-N conversion ratios vary from 1–7% to 15–24% under fuel-rich and fuel-lean conditions, respectively. The char-N conversion ratios are 11–28% and 30–50% under fuel-rich and fuel-lean conditions, respectively. The influences of temperature on the conversion of volatile-N to NO under fuel-rich and fuel-lean conditions are contrary. A significant difference for char-N conversion in fuel-rich and fuel-lean conditions is observed. The experimental data of recycle NO reduction indicate that the reduction of recycle NO by gas-phase reaction can be enhanced by volatile-N addition in fuel-lean condition at high temperature, while in fuel-rich condition, the volatile-N influence cancelled out and the overall impact is small. NO/char reaction competes with the conversion of fuel-N to NO at higher temperatures.     

Quantifying the effect of CO2 gasification on pulverized coal char oxy-fuel combustion

Previous research has provided strong evidence that CO₂ and H₂O gasification reactions can provide non-negligible contributions to the consumption rates of pulverized coal (pc) char during combustion, particularly in oxy-fuel environments. Fully quantifying the contribution of these gasification reactions has proven to be difficult, due to the dearth of knowledge of gasification rates at the elevated particle temperatures associated with typical pc char combustion processes, as well as the complex interaction of oxidation and gasification reactions. Gasification reactions tend to become more important at higher char particle temperatures (because of their high activation energy) and they tend to reduce pc oxidation due to their endothermicity (i.e. cooling effect). The work reported here attempts to quantify the influence of the gasification reaction of CO₂ in a rigorous manner by combining experimental measurements of the particle temperatures and consumption rates of size-classified pc char particles in tailored oxy-fuel environments with simulations from a detailed reacting porous particle model. The results demonstrate that a specific gasification reaction rate relative to the oxidation rate (within an accuracy of approximately +/- 20% of the pre-exponential value), is consistent with the experimentally measured char particle temperatures and burnout rates in oxy-fuel combustion environments. Conversely, the results also show, in agreement with past calculations, that it is extremely difficult to construct a set of kinetics that does not substantially overpredict particle temperature increase in strongly oxygen-enriched N₂ environments. This latter result is believed to result from deficiencies in standard oxidation mechanisms that fail to account for falloff in char oxidation rates at high temperatures.     

Effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions

The effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions was studied by single particle experiments and modelling. Experiments of pine and beech wood char conversion were carried out in a single particle combustor under conditions of 1473-1723 K, 0.0-10.5% O₂, and 25-42% H₂O. A comprehensive progressive char conversion model, including heterogeneous reactions (char oxidation and char gasification with CO₂ and H₂O), homogeneous reactions (CO oxidation, water-gas shift reaction, and H₂ oxidation) in the particle boundary layer, particle shrinkage, and external and internal heat and mass transfer, was developed. The modelling results are in good agreement with both experimental char conversion time and particle size evolution in the presence of oxygen, while larger deviations are found for the gasification experiments. The modelling results show that the char oxidation is limited by mass transfer, while the char gasification is controlled by both mass transfer and gasification kinetics at the investigated conditions. A sensitivity analysis shows that the CO oxidation in the boundary layer and the gasification kinetics influence significantly the char conversion time, while the water-gas shift reaction and H₂ oxidation have only a small effect. Analysis of the sensitive parameters on the char conversion process under a typical pulverized biomass combustion condition (4% O₂, 13% CO₂, 13% H₂O), shows that the char gasification reactions contribute significantly to char conversion, especially for millimeter-sized biomass char particles at high temperatures.     

Fundamental investigation of NOx formation during oxy-fuel combustion of pulverized coal

NO_x formation was measured during combustion of pulverized coals and pulverized coal char in N₂ and CO₂ environments under isothermal and nearly constant oxygen conditions (i.e. using dilute coal loading). Three different oxygen concentrations (12% O₂, 24% O₂, and 36% O₂) and two representative US coals were investigated, at a gas temperature of 1050 °C. To investigate the importance of NO reburn reactions, experiments were also performed with an elevated concentration (550 ppm) of NO in the gases into which the coal was introduced. For low levels of background NO, the fractional fuel-nitrogen conversion to NO_x increases dramatically with increasing bath gas oxygen content, for both N₂ and CO₂ environments, though the fuel conversion is generally lower in CO₂ environments. Char N conversion is lower than volatile N conversion, especially for elevated O₂ concentrations. These results highlight the importance of the volatile flame and char combustion temperatures on NO_x formation. For the high background NO_x condition, net NO_x production is only observed in the 36% O₂ environment. Under these dilute loading conditions, NO reburn is found to be between 20% and 40%, depending on the type of coal, the use of N₂ or CO₂ diluent, the bulk O₂ concentration, and whether or not one considers reburn of volatile-NO_x. This dataset provides a unique opportunity to understand and differentiate the different sources and sinks of NO_x under oxy-fuel combustion conditions.     

Experimental investigation of NOx emission and ash-related issues in ammonia/coal/biomass co-combustion in a 25-kW down-fired furnace

Co-firing ammonia in coal units is a promising approach for the phasedown of coal power. In this paper, we demonstrate the feasibility of burning ammonia with coal and biomass in a 25- kW down-fired furnace with a swirl-stabilized burner. Ammonia is injected from the central tube at thermal ratios ranging from 0 to30% and can be completely burnt out in most co-firing cases. We investigate the NO_x emission, unburnt carbon in fly ash, particulate matter formation and ash deposition behaviors when co-firing NH₃ with either SH lignite coal or the coal/biomass blend. With a fixed air staging ratio, the NO_x emission increases linearly with the NH₃ fuel ratio. By increasing the percentage of secondary air, the emitted NO_x can be reduced to 300 ppm with an NH₃ thermal ratio of 30%. The unburnt carbon is affected by NH₃ addition in a complex manner. With a 30% (thermal) NH₃ addition, the unburnt carbon increases from 0.4% to 5.6% for the SH coal mainly due to a temperature drop, but decreases from 2.2% to 0.7% for the SH coal/biomass blend. As for the ash-related issues, the addition of NH₃ to either coal or coal/biomass blend is found to alleviate both the fouling intensity and the ultrafine particulate matter formation ability. This is a major advantage over biomass combustion.     

Pressurized oxy-fuel combustion of a char particle in the fluidized bed combustor

Pressurized oxy-fuel combustion of coal in fluidized bed (FB) holds the potential to realize low-cost CO₂ capture. However, the fundamental study in this manner is still rare due to the difficult access to the pressurized oxy-FB combustion tests. In this work, the experimental study of single char combustion was firstly conducted in a visualized pressurized FB combustor under various operating conditions. Then an experimentally verified particle-scale char combustion model was developed to reveal the dependence of char combustion on parameters. Results showed that the char conversion was accelerated with the increase of pressure, mainly due to the high oxygen diffusion and char gasification. The gasification played a non-negligible role in pressurized oxy-fuel combustion, especially under high oxygen concentration and bed temperature. Increasing oxygen concentration and bed temperature not only promotes the char oxidation rate and particle temperature, but also increases the gasification rate and the share of char conversion via gasification, resulting in shortening the burnout time of char. In addition, a higher fluidization number lowered both the burnout time and peak temperature of char particle, due to the simultaneous improvement of mass and heat transfer. The influences of char size and fluidization number on char gasification conversion ratio are very weak. In addition, the quantitative analysis of the influence of different operating parameters on the combustion process was obtained by model sensitivity analysis.     

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.     

Effect of pyrolysis conditions on gasification reactivity of woody biomass-derived char

The effect of pyrolysis conditions on char reactivity has been studied using Raman spectroscopy. This paper reports on the relationship between the properties of biomass char and the gasification rate. The gasification kinetics of biomass char have been revealed by measuring the rate of weight loss during its reaction with CO₂ as a function of temperature. First-order kinetic rate constants are determined by fitting the weight loss data using a random pore model. The relationship between the char structure and CO₂ gasification reactivity was investigated in the range of 15–600 °C/min at a constant pyrolysis pressure (0.1 MPa), and 0.1–3.0 MPa at a constant heating rate (15 °C/min). The experimental results reveal that the reactivity of biomass char is determined by the pyrolysis condition. The CO₂ gasification rates in char generated at 0.1 MPa exhibited approximately twice the values as compared to those obtained at 3 MPa. This is because the uniformity of the carbonaceous structure increases with the pyrolysis pressure. The uniformity of carbonaceous structures would affect the CO₂ gasification reactivity, and the decreasing uniformity would lead to the progression of cavities on the char surface during the CO₂ gasification process. The gasification rate of biomass char increases with the heating rate at pyrolysis. This is due to the coarseness (surface morphology) of biomass char and rough texture, which increases with the heating rate.     

Comparing reaction orders of anthracite chars with bituminous coal chars at high temperature oxidation conditions

The influence of concentration of oxygen on the oxidation rates of 5 anthracite chars is investigated at gas temperatures ranging from 1223 K to 1673 K. Reaction orders and kinetic parameters are determined with a multivariable optimization method in which modeled burnout profiles are fitted to experimental burnout profiles from a 4 m isothermal plug flow reactor operating at industrially realistic heating rates, i.e., 10⁴–10⁵ K/s. The determined reaction orders are compared to reaction orders of 10 bituminous coal chars investigated at similar conditions in a previous study. The results show that the optimized reaction order of the anthracite chars is zero, while the reaction order of the bituminous coal char is one. The difference in the reaction orders cannot be explained by using the two semi-global oxidation reactions: C(O) + O₂ → CO/CO₂ and C(O) → CO. However, by also considering 2C(O) → CO₂ + C as a possible reaction step, the reaction order difference between the anthracite chars and the bituminous coal chars can be explained. In addition, a first attempt to apply the same multivariable optimization method to determine the reaction order for a biomass char is presented.     

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.     

Effect of high CO2 concentration on char formation through mineral reaction during biomass pyrolysis

O₂/CO₂ combustion has attracted considerable attention as a promising technology for CO₂ capture. Using biomass for fuel is considered carbon neutral, and O₂/CO₂ biomass combustion can mitigate the deleterious environmental effect of greenhouse. In this study, the effect of CO₂, the main component gas in O₂/CO₂ combustion, on the pyrolysis characteristics of biomass is investigated. Cellulose, lignin, and metal-depleted lignin pyrolysis experiments were performed using a thermobalance. Information on the surface chemistry of the chars was obtained by Fourier transform infrared (FTIR) spectroscopy to investigate changes in the surface chemistry during pyrolysis under different surrounding gasses. When the temperature increased to 1073 K at heating rate of 1 K s^?1, the char yield of lignin in the presence of CO₂ increased by about 10% compared with that under Ar. However, for cellulose and metal-depleted lignin, no significant difference appeared between pyrolysis under CO₂ and that under Ar. FT-IR showed that a strong peak corresponding to carbonate ions appeared in the char derived from lignin under CO₂. Therefore, salts such as Na₂CO₃ or K₂CO₃ formed during the lignin pyrolysis under CO₂. At around 1650–1770 cm^?1, a significant difference appeared in the FTIR spectra of chars formed under CO₂ and those formed under Ar. C=O groups not associated with an aromatic ring were found only in chars formed under CO₂. It was suggested that these salts affected the char formation reaction, in that the char formed during lignin pyrolysis under CO₂ had unique chemical bands that did not appear in the lignin-derived char prepared under Ar.     

Experimental study on co-firing characteristics of ammonia with pulverized coal in a staged combustion drop tube furnace

Utilizing ammonia as a co-firing fuel to replace amounts of fossil fuel seems a feasible solution to reduce carbon emissions in existing pulverized coal-fired power plants. However, there are some problems needed to be considered when treating ammonia as a fuel, such as low flame stability, low combustion efficiency, and high NO_x emission. In this study, the co-firing characteristics of ammonia with pulverized coal are studied in a drop tube furnace with staged combustion strategy. Results showed that staged combustion would play a key role in reducing NO_x emissions by reducing the production of char-NO_x and fuel(NH₃)-NO_x simultaneously. Furthermore, the effects of different ammonia co-firing methods on the flue gas properties and unburned carbon contents were compared to achieve both efficient combustion and low NO_x emission. It was found that when ammonia was injected into 300 mm downstream under the condition of 20% co-firing, lower NO_x emission and unburnt carbon content than those of pure coal combustion can be achieved. This is probably caused by a combined effect of a high local equivalence ratio of NH₃/air and the prominent denitration effect of NH₃ in the vicinity of the NH₃ downstream injection location. In addition, NO_x emissions can be kept at approximately the same level as coal combustion when the co-firing ratio is below 30%. And the influence of reaction temperature on NO_x emissions is closely associated with the denitration efficiency of the NH₃. Almost no ammonia slip has been detected for any injection methods and co-firing ratio in the studied conditions. Thus, it can be confirmed that ammonia can be used as an alternative fuel to realize CO₂ reduction without extensive retrofitting works. And the NO_x emission can be reduced by producing a locally NH₃ flame zone with a high equivalence ratio as well as ensuring adequate residence time.     

On the reaction mechanism of CO2 reforming of methane over a bed of coal char

CO₂ reforming of methane was studied over a bed of coal char in a fixed bed reactor at temperatures between 1073 and 1223 K and atmospheric pressure with a feed composition of CH₄/CO₂/N₂ in the ratio of 1:1:8. Experimental results showed that the char was an effective catalyst for the production of syngas with a maximum H₂/CO ratio of one. It was also found that high H₂/CO ratios were favoured by low pressures and moderate to high temperatures. These results are supported by thermodynamic calculations. A mechanism of seven overall reactions was studied and three catalytic reactions of CH₄ decomposition, char gasification and the Boudouard reaction was identified as being of major importance. The first reaction produces carbon and H₂, the second consumes carbon, and the third (the Boudouard reaction) converts CO₂ to CO while consuming carbon. Equilibrium calculations and experimental results showed that any water present reacts to form H₂ and carbon oxides in the range of temperatures and pressures studied. Carbon deposition over the char bed is the major cause of deactivation. The rate of carbon formation depends on the kinetic balance between the surface reaction of the adsorbed hydrocarbons with oxygen containing species and the further dissociation of the hydrocarbon.     

A comparative study of FESEM and EDX analyses of Datong coal in N2 and CO2 environments

Field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and Brunauer Emmett Teller surface area analyses of char produced in CO₂ and N₂ environments in a thermo-gravimetric analyzer, using thermo-plus II software, were investigated under different parametric conditions. These conditions include temperature, flow rate variations etc. for the implementation of oxy-fuel combustion technology. It was observed that, at high temperatures and low flow rates, the mass loss rate of coal in CO₂ was higher than in that of a N₂ environment. This may be due to one additional step of coal gasification i.e. char gasification by CO₂ at higher temperature. More importantly, during the reaction with CO₂ the formations of perfectly hexagonal nanorods at the particular temperature of 773 K were observed. However, the amount of these nanorods decreases and the dimensions i.e. size and shape change (smaller aspect ratio) with the increase of flow rate and temperature as well. The formation of these nanorods are attracted much because of their peculiar properties and potential applications in functional nano-devices and environmentally clean energy purposes i.e. CO₂ capturing.     

Measurement and kinetics of elemental and atomic potassium release from a burning biomass pellet

Combining polarizing-filtered planar laser-induced fluorescence (PLIF) with simultaneous laser absorption, quantitative laser-induced breakdown spectroscopy (LIBS) and two-color pyrometry, the potassium release during the combustion of biomass fuels (corn straw and poplar) has been investigated. The temporal release profiles of volatile atomic potassium and potassium compounds from a corn straw show a single peak. The woody biomass, poplar, produces a dual-maxima distribution for potassium and potassium compounds. For both biomass samples, the highest concentrations of released atomic potassium and potassium compounds occur in the devolatilization stage. The mass ratios between volatile atomic potassium and potassium compounds in the corn straw and poplar cases are 0.77% and 0.79%, respectively. These values agree well with chemical equilibrium predictions that 0.68% of total potassium will be in atomic form. A two-step kinetic model of potassium release has been developed, which gives better predictions during the devolatilization stage than the existing single-step model. Finally, a map of potassium transformation processes during combustion is developed. Starting with inorganic and organic potassium, there are eight proposed transformation pathways including five proposed release pathways that occur during the combustion. The pathways describe the transformation of potassium between the fuel volatile matter, char, and ash. Potassium release during the devolatilization stage is due to pyrolysis and evaporation; during the char burnout stage, potassium release is due to char oxidation and decomposition; and during the ash cooking stage, potassium release is caused by reactions between the ash and H₂O in the co-flow.     

Heterogeneous fixation of N2: Investigation of a novel mechanism for formation of NO

Formation of NO initiated by heterogeneous fixation of N₂ during pyrolysis is investigated experimentally and theoretically. The experiments were conducted with beech wood as well as with the pure biomass components cellulose, xylan, and lignin. The NO formation during char oxidation was recorded as function of pyrolysis atmosphere (N₂ or Ar), pyrolysis temperature (700–1050 °C), and oxidizing atmosphere (O₂ in N₂ or Ar). The results confirm earlier reports that biomass char may be enriched in N during pyrolysis at 900 °C and above. The N-uptake involves re-capture of N-volatiles as well as uptake of N₂. During char oxidation, the captured N is partly oxidized to NO, resulting in increased NO formation. The NO yield from oxidation of beech wood char made in N₂ increases with pyrolysis temperature, and is about a factor of two higher at 1050 °C than the corresponding yield from chars made in Ar. The experiments with pure materials show that the lignin char has the strongest ability to form NO from uptake of N₂, while xylan char forms only small amounts of NO from N₂. Density Functional Theory (DFT) calculations on model chars have revealed a number of chemisorption sites for N₂, many of which are weakly bound and therefore expected to have a short half-life at the higher pyrolysis temperatures. However, the chemisorption of N₂ across a single ring of the armchair surface was found to have an activation energy of 344 ± 30 kJ mol⁻¹ and form a stable, exothermic product with cyano groups. This demonstrates that at least one channel exists for the high-temperature incorporation of N₂ into a char which could give rise to the observed increase in NO release in subsequent char oxidation.