An investigation of the thermal and catalytic behaviour of potassium in biomass combustion

Potassium, a key nutrient in biomass growth, contributes to problematic ash chemistry and corrosion in combustion. This study seeks to examine the behaviour and fate of potassium in biomass combustion under high temperature flame conditions. A model to predict potassium release is presented. Short rotation willow coppice was treated to reduce metals, by water-washing, and remove them, by demineralisation, and then potassium was doped into the demineralised sample. The resultant fuels have been studied for their combustion behaviours in methane–air flames, both as suspended, moving particles, and as stationary, supported particles, using high speed digital video. In the latter case, potassium release was measured simultaneously by emission spectroscopy. In both experiments, potassium was seen to catalyse devolatilisation, and for the stationary particles it was possible to detect potassium catalysis in the char burn-out rates. Demineralised willow was seen to melt in the flame and combustion resembled heavy oil combustion, rather than solid fuel combustion. The residual char was extremely slow to burn-out. In the potassium-doped particles, potassium was seen to evolve over three regimes, devolatilisation, char burn-out and, less significantly, during ash cooking. The first two evolution processes have been modelled using an apparent first order devolatilisation rate for the first stage, and a KOH evaporation model for the second stage.     

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.     

Experimental and numerical investigations on the interactions of volatile flame and char combustion of a coal particle

The model that takes chemical reactions, heat and mass transfers in the boundary layer of the particle into account simultaneously, is developed for simulating the combustion of a pulverized coal particle. The FTIR in situ temperature-measurements and the comparison between numerical simulations for the pulverized coal and the devolatilized char show that the volatile flame induces the combustion of the primary product of surface oxidation CO. Due to the influence of volatile flame, the char particle can be ignited at temperature lower than its heterogeneous ignition temperature, which elucidates the physical essence of joint hetero-homogeneous ignition mode discovered by Jüntgen.     

Modeling of the submicron particles formation and initial layer ash deposition during high temperature oxy-coal combustion

The future use of coal as a fuel for power generation in the US depends on the availability of financially viable technologies for capture and storage of CO₂ emissions from power plants. Key second-generation candidates for CO₂ capture include high temperature and pressurized oxy-firing of coal, which has the potential to increase efficiency, lower capital costs, avoid air ingress and reduce oxygen requirements. However, unquantified challenges, such as flame behavior, heat transfer, ash transformation, ash deposition and char oxidation, still exist for those technologies. This study specifically focuses on the formation of submicron particles and initial layer ash deposition during high temperature oxy-coal combustion. Previous work has shown that the initial layer deposits are mainly formed of submicron size ash aerosols transported by thermophoresis. Unfortunately, the importance of submicron particle deposition has not received much attention, probably due to the insignificant deposit mass and difficulty in prediction of the submicron particles formation. In this work, models including mineral matter vaporization model, scavenging model and deposition model are developed and applied into a three-dimensional CFD framework to predict the submicron particles formation and subsequent initial layer deposits formation. The model results are comparable to experimental data. The merits of this work are that it has led to the development of a novel approach to predict both submicron particle formation and initial layer ash deposition during oxy-coal combustion.     

Single particle ignition and combustion of pulverized pine wood,wheat straw,rice husk and grape pomace

This work examines the combustion behavior of single pulverized biomass particles from ignition to early stages of char oxidation. The biomass residues investigated were pine wood, wheat straw, rice husk and grape pomace. The biomass particles, in the size range 224–250 µm, were injected upward into a confined region with hot combustion products, produced by a flat flame McKenna burner, with a mean temperature of 1610 K and a mean O₂ concentration of 6.5 vol%. Temporally and spectrally resolved images of the single burning particles were recorded with an intensified charge-coupled device camera equipped with different band-pass spectral filters. Data are reported for CH*, C₂*, Na* and K* chemiluminescence, and thermal radiation from soot and char burning particles. The data on CH* and C₂* chemiluminescence and soot thermal radiation permits to identify important differences between the ignition delay time, volatiles combustion time and soot formation propensity of the four biomass residues, which are mainly affected by their volatile matter content. The Na* and K* emission signals follow the same trends of the CH* and C₂* emission signals until the end of the volatiles combustion stage, beyond which, unlike the CH* and C₂* emission signals, they persist owing to their release from the char burning particles. Moreover, during the volatiles combustion stage, the Na*/CH* and K*/CH* ratios present constant values for each biomass residue. The CH* and thermal radiation emission data suggest that all biomass char particles experienced heterogeneous oxidation at or immediately after the extinction of the homogeneous volatiles combustion.     

Large eddy simulation of piloted pulverised coal combustion using extended flamelet/progress variable model

An extended flamelet/progress variable (EFPV) model for simulating pulverised coal combustion (PCC) in the context of large eddy simulation (LES) is proposed, in which devolatilisation, char surface reaction and radiation are all taken into account. The pulverised coal particles are tracked in the Lagrangian framework with various sub-models and the sub-grid scale (SGS) effects of turbulent velocity and scalar fluctuations on the coal particles are modelled by the velocity-scalar joint filtered density function (VSJFDF) model. The presented model is then evaluated by LES of an experimental piloted coal jet flame and comparing the numerical results with the experimental data and the results from the eddy break up (EBU) model. Detailed quantitative comparisons are carried out. It is found that the proposed model performs much better than the EBU model on radial velocity and species concentrations predictions. Comparing against the adiabatic counterpart, we find that the predicted temperature is evidently lowered and agrees well with the experimental data if the conditional sampling method is adopted.     

Pore-Resolving Simulations of Biomass Char Particle Combustion

Biomass char morphology affects combustion behavior at the particle scale for zone II conditions, in which both heterogeneous reaction and intra-particle diffusion govern the overall rate. Furthermore, particle-scale processes affect reactor-scale outputs, and reactor-scale simulations are sensitive to particle-scale models. However, most char particle combustion models employ coarse-grained, effective-continuum approaches, which treat all porosity at the subgrid-scale. Effective-continuum approaches are not valid or accurate in the presence of large, irregular pores which can approach the size of the particle. A 3-D, pore-resolving CFD simulation approach using real biomass char particle geometries obtained from X-ray micro-computed tomography (micro-CT) is therefore used to examine the impact of morphology on zone II combustion for pulverized (∼100 µm) biomass char particles for the first time. In contrast to larger, millimeter to centimeter sized particles, the sub-millimeter, high aspect ratio biomass char particles exhibited localized reactant penetration into the innermost regions of the particles, facilitated by the presence of large pores connected to the external surface. The oxygen mole fraction distributions were governed by the large pore morphology, were non-monotonic with distance from the surface, and achieved minima in thick microporous char regions surrounding the large pores. A comparison between the pore-resolving simulation and an equivalent, spatially resolved, effective-continuum simulation revealed that even in the microporous char, the effective-continuum model underpredicted reactant penetration. A careful comparison was then performed between 30 pore-resolving particle simulations and several effectiveness factor models that employed particle-specific parameters. Commonly used uniform cylinder models significantly underpredicted effectiveness factors for these real pulverized pine char particles, while accessible hollow cylinder models achieved less than 10% relative error when averaged over all 30 particles.     

Transported PDF simulation of turbulent CH4/H2 flames under MILD conditions with particle-level sensitivity analysis

Transported probability density function (TPDF) simulation with sensitivity analysis has been conducted for turbulent non-premixed CH₄/H₂ flames of the jet-into-hot-coflow (JHC) burner, which is a typical model to emulate moderate or intense low oxygen dilution combustion (MILD). Specifically, two cases with different levels of oxygen in the coflow stream, namely HM1 and HM3, are simulated to reveal the differences between MILD and hot-temperature combustion. The TPDF simulation well predicts the temperature and species distributions including those of OH, CO and NO for both cases with a 25-species mechanism. The reduced reaction activity in HM1 as reflected in the peak OH concentration is well correlated to the reduced oxygen in the coflow stream. The particle-level local sensitivities with respect to mixing and chemical reaction further show dramatic differences in the flame characteristics. HM1 is less sensitive to mixing and reaction parameters than HM3 due to the suppressed combustion process. Specifically, for HM1 the sensitivities to mixing and chemical reactions have comparable magnitude, indicating that the combustion progress is controlled by both mixing and reaction in MILD combustion. For HM3, there is however a change in the combustion mode: during the flame initialization, the combustion progress is more sensitive to chemical reactions, indicating that finite-rate chemistry is the controlling process during the autoignition process for flame stabilization; at further downstream where the flame has established, the combustion progress is controlled by mixing, which is characteristic of nonpremixed flames. An examination of the particles with the largest sensitivities reveals the difference in the controlling mixtures for flame stabilization, namely, the stoichiometric mixtures are important for HM1, whereas, fuel-lean mixtures are controlling for HM3. The study demonstrates the potential of TPDF simulations with sensitivity analysis to investigate the effects of finite-rate chemistry on the flame characteristics and emissions, and reveal the controlling physio-chemical processes in MILD combustion.     

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.     

An improved model of fine particulate matter formation coupling the mechanism of mineral coalescence and char fragmentation during pulverized coal combustion

An improved model of fine particulate matter formation coupling the mechanism of mineral coalescence and char fragmentation under different pulverized coal combustion environments has been constructed. Firstly, based on the theoretical model of char fragmentation and percolation, the included minerals with different types and particle sizes are constructed in the model, and a three-dimensional char particle sub-model is established. And the type, content and particle size distribution of included minerals are introduced as input parameters by using computer controlled scanning electron microscopy (CCSEM) technology. All of the above makes it more in line with the actual distribution of the included minerals. Then a sub-model of char fragmentation is built based on the sub-model of the char particle. And considering the influence of char combustion reaction on the particle formation process and melting characteristics of included minerals, a sub-model of mineral melting coalescence under different combustion environments is established. Finally, based on this improved model, we compared the calculation results with the experimental data and the calculation results of the traditional model. Fully considering the process of mineral coalescence and char fragmentation, which contains the characteristics of different included minerals, the results show that the newly established model has a good fitting effect for the experiment and is closer to the actual process of char particle combustion to generate particles. By the new model, the influence of the factors (mineral content, particle size distribution and porosity) on the formation of particulate matter is preliminarily analyzed.     

Particle temperature and potassium release during combustion of single pulverized biomass char particles

This work investigated the combustion characteristics of single pulverized biomass-derived char particles. The char particles, in the size range 224–250 µm, were prepared in a drop tube furnace at pyrolysis temperatures of 1273 or 1473 K from four types of biomass particles – wheat straw, grape pomace, kiwi branches and rice husk. Subsequently, the char particles were injected upward into a confined region of hot combustion products produced by flat flames stabilized on a McKenna burner, with mean temperatures of 1460, 1580 and 1670 K and mean O₂ concentrations of 4.5, 6.5 and 8.5 vol%. The data reported include particle temperature, obtained using a two-color pyrometry technique, and potassium release rate, measured using a laser-induced photofragmentation fluorescence imaging technique. In addition, particle ignition delay time and burning time, obtained from the temporal evolution of the thermal radiation intensity of the burning char particles, are also reported. The results indicated that ignition of the char particles occurs simultaneously with the starting of the potassium release, then the particle burning intensity increases rapidly until it reaches a maximum, after which both the particle temperature and the potassium release rate remain approximately constant until the end of the char oxidation process. The char ignition process is temperature controlled, and the char oxidation process is oxygen diffusion controlled, with the total potassium release being independent of the oxygen concentration and the temperature of the combustion products. The combustion behavior of the chars studied is more affected by the char type than by the conditions used to prepare them.     

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.     

A three mixture fraction flamelet model for multi-stream laminar pulverized coal combustion

A three mixture fraction flamelet model is proposed for multi-stream laminar pulverized coal combustion. The technique of coordinate transformation is utilized to map the flamelet solutions from a unit pyramid space into a unit cubic space to improve the stability of the simulation. The validity of the three mixture fraction flamelet model was assessed on different configurations, including a laminar counterflow pulverized coal/methane flame and a laminar piloted pulverized coal jet flame. The flamelet predictions were compared to the reference results of the detailed chemistry solutions. For the counterflow flame, it was found that the flame temperature and major species mass fractions are correctly predicted by the three mixture fraction flamelet model. However, discrepancies are observed for combustion-mode-sensitive species such as CO and H₂ in the premixed combustion region. The thermo-chemical quantities in the char surface reaction zone cannot be correctly predicted if the mixing between the char off-gas stream and other streams is neglected. For the piloted jet flame, it was shown that the stable thermo-chemical variables can be correctly predicted at the upper and middle stream locations. However, at the downstream location, discrepancies can be observed in certain regions. Overall, the validity of the three mixture fraction flamelet model for multi-stream pulverized coal combustion is confirmed and its performance in turbulent pulverized coal combustion will be tested in future work.     

The effect of potassium bromide and sodium carbonate on coal char combustion reactivity

The addition of halogens, particularly iodine, to the gas during coal char oxidation has been used in previous studies to quench gas-phase chemistry, thereby allowing one to separate the effects of homogeneous and heterogeneous reactions. Halogen addition suppresses the gas-phase radicals to near-equilibrium levels. A similar effect can be expected from other compounds with high efficiency as fire suppressants, such as alkali metals. The effectiveness of the use of additives in distinguishing homogeneous and heterogeneous reactions during char oxidation relies on the assumption that radicals are suppressed while heterogeneous reactions occurring on the char surface are not affected. The present work tests this assumption for potassium bromide (KBr) and sodium carbonate (Na₂CO₃) reacting with a pulverized eastern bituminous coal char during oxidation. An increase in CO and a slight reduction in particle temperature were observed with the addition of KBr, consistent with known effects of halogens on gas-phase chemistry. An increase in particle size was also observed with the KBr addition. This observation and the results of model calculations suggest that there is significant incorporation of liquid KBr on the char surface under the conditions examined. With Na₂CO₃ addition, the particle temperature did not change, the particle size showed a slight decrease, and CO production increased. Although the mechanisms for Na interaction with radicals at combustion conditions are not well established, char oxidation modeling suggests that a decrease in OH concentration in the particle boundary layer is the cause for the observed increase in CO production. It is concluded that Na₂CO₃ has clear advantages over KBr for inhibiting gas-phase chemistry without affecting char oxidation for the conditions investigated here.     

A thermogravimetric method for the measurement of CO/CO2 ratio at the surface of carbon during combustion

This work presents a new method of measuring the CO/CO₂ ratio at the surface of carbon particles during combustion. This thermogravimetric method deduces the ratio of CO to CO₂ by comparing the rate of consumption of carbon with the rate of oxidation of an external reference material with fast oxidation kinetics, in this case Cu. The method is useful when combustion is controlled by external mass transfer, commonly encountered in large-scale processes. The viability of this method has been demonstrated experimentally with graphite and a lignite char. It was found that in an atmosphere of ～ 1% O₂, the graphite produced CO₂ between 700 and 900 °C whilst the lignite char produced a mixture of CO and CO₂ between 700 and 800 °C with the proportion of CO increasing with temperature, and above 850 °C, only CO was produced. It was also found that for this particular lignite char, the ratio of CO/CO₂ increased with decreasing pO₂ in the environment.     

Prediction of NO in turbulent diffusion flames using Eulerian particle flamelet model

The combustion characteristics for the turbulent diffusion flames using the unsteady flamelet concept have been numerically investigated. The Favre-averaged Navier–Stokes equations are solved by a finite volume method of SIMPLE type that incorporates the laminar flamelet concept with a modified k ? ε turbulence model. The NO formation is estimated by solving the Eulerian particle transport equations in a postprocessing mode. Two test problems are considered: CH₄/H₂/N₂ jet flame and CH₄/H₂ stabilised bluff body flame. The temperature and species profiles are well captured by the flamelet model. Two different chemical mechanisms (GRI 2.11 and 3.0) give nearly identical results for temperature and species except NO. The GRI 3.0 gives significantly higher NO levels compared to the GRI 2.11. This is mainly attributed to the difference in NO formation by the prompt mechanism. The NO formation is sensitive to the number of flamelet particles. The NO levels for two test flames do not change when the flamelet particle number exceeds six.     

Implementation of an advanced fixed sectional aerosol dynamics model with soot aggregate formation in a laminar methane/air coflow diffusion flame

An advanced fixed sectional aerosol dynamics model describing the evolution of soot particles under simultaneous nucleation, coagulation, surface growth and oxidation processes is successfully implemented to model soot formation in a two-dimensional laminar axisymmetric coflow methane/air diffusion flame. This fixed sectional model takes into account soot aggregate formation and is able to provide soot aggregate and primary particle size distributions. Soot nucleation, surface growth and oxidation steps are based on the model of Fairweather et al. Soot equations are solved simultaneously to ensure convergence. The numerically calculated flame temperature, species concentrations and soot volume fraction are in good agreement with the experimental data in the literature. The structures of soot aggregates are determined by the nucleation, coagulation, surface growth and oxidation processes. The result of the soot aggregate size distribution function shows that the aggregate number density is dominated by small aggregates while the aggregate mass density is generally dominated by aggregates of intermediate size. Parallel computation with the domain decomposition method is employed to speed up the calculation. Three different domain decomposition schemes are discussed and compared. Using 12 processors, a speed-up of almost 10 is achieved which makes it feasible to model soot formation in laminar coflow diffusion flames with detailed chemistry and detailed aerosol dynamics.     

Combustion and emission modelling of a direct-injection spark-ignition engine by combining flamelet models for premixed and diffusion flames

The combustion and emission production processes of a DISI (direct-injection spark-ignition) engine were modelled by combining flamelet models for premixed and diffusion flames. A new surrogate fuel was proposed to approximate the complicated composition of real gasoline. In contrast to simpler conventional models, the fuel was modelled as a ternary mixture of three hydrocarbons: iso-octane, n-heptane and toluene. Turbulent flame propagation in a partially premixed field was modelled by a premixed flamelet model. The mass fractions of the detailed composition of species in burnt gas were predicted by a diffusion flamelet model. For the pollutant formation modelling, a two-step oxidation of CO and H₂ was used to simulate the secondary diffusion flame. The extended Zeldovich mechanism was used to model NOx formation, while a phenomenological model was used to model soot formation. This model was initially applied to a simple geometry to investigate the fundamentals of the model's behaviour, after which three-dimensional computational fluid dynamic (CFD) simulations were performed in a realistic engine geometry.