Analysis of model dimensionality,particle shrinkage,boundary layer reactions on particle-scale modelling of biomass char conversion under pulverized fuel combustion conditions

In this work, the effects of model dimensionality, particle shrinkage, and boundary layer reactions on particle-scale modelling of biomass char conversion under pulverized fuel combustion conditions have been analysed by using six models: zero-dimensional models with constant particle size (0D_Cons) or shrinking particle size (0D_SPM), one-dimensional models with/without considering particle shrinkage (1D_Cons/1D_SPM), and 1D_Cons and 1D_SPM with considering boundary layer reactions (1D_Cons_BH and 1D_SPM_BH). A comparison with existing experimental data shows that the 1D_SPM_BH model with consideration of intra-particle heat and mass transfer, particle shrinkage, and boundary layer reactions is an appropriate model to describe biomass char conversion over a wide range of conditions. The 0D_Cons model is a good approximation for the conditions of small particle size (< 1 mm) at 1273–1473 K, but overestimates the char conversion rate for larger biomass char particle or at high temperatures (regime III). The 0D_SPM model gives a reasonable prediction on char conversion time but predicts a larger contribution of reaction between char and O₂ as compared to the 1D_SPM_BH model. The consideration of intra-particle heat and mass transfer in particle-scale modelling (1D_Cons and 1D_SPM) is beneficial to improving the model prediction of char conversion time and the contributions of char oxidation and gasification reactions. The boundary layer reactions have a significant effect on the prediction of char conversion for large particles (> 1 mm) and high temperatures (> 1473 K). An implication for the selection of a particle-scale model in CFD modelling is also given.     

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.     

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.     

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.     

Attrition of lignite char under fluidized bed gasification conditions: The effect of carbon conversion

The effect of carbon conversion on the attrition of lignite char particles during fluidized bed gasification by CO₂ was studied in a lab-scale apparatus. The influence of bed temperature and inlet CO₂ concentration on carbon conversion and, consequently, on attrition was studied. The mechanical resistance of the char particles was also characterized at different stages of char conversion by specific attrition experiments. A predictive kinetic model for CO₂ gasification of the lignite char was developed from the experimental results, that was able to correctly predict the evolution of carbon conversion versus time. On this basis a semi-empirical model was developed in order to simulate the evolution of carbon elutriation rate with carbon conversion degree, i.e. the gasification-assisted attrition enhancement effect.     

Characterizing char particle fragmentation during pulverized coal combustion

A particle population balance model was developed to predict the oxidation characteristics of an ensemble of char particles exposed to an environment in which their overall burning rates are controlled by the combined effects of oxygen diffusion through particle pores and chemical reactions (the zone II burning regime). The model allows for changes in particle size due to burning at the external surface, changes in particle apparent density due to internal burning at pore walls, and changes in the sizes and apparent densities of particles due to percolation type fragmentation. In percolation type fragmentation, fragments of all sizes less than that of the fragmenting particle are produced. The model follows the conversion of particles burning in a gaseous environment of specified temperature and oxygen content. The extent of conversion and particle size, apparent density, and temperature distributions are predicted in time.Experiments were performed in an entrained flow reactor to obtain the size and apparent density data needed to adjust model parameters. Pulverized Wyodak coal particles were injected into the reactor and char samples were extracted at selected residence times. The particle size distributions and apparent densities were measured for each sample extracted. The intrinsic chemical reactivity of the char to oxygen was also measured in experiments performed in a thermogravimetric analyzer. Data were used to adjust rate coefficients in a six-step reaction mechanism used to describe the oxidation process.Calculations made allowing for fragmentation with variations in the apparent densities of fragments yield the type of size, apparent density, and temperature distributions observed experimentally. These distributions broaden with increased char conversion in a manner that can only be predicted when fragmentation is accounted for with variations in fragment apparent density as well as size. The model also yields the type of ash size distributions observed experimentally.     

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.     

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.     

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.     

Prediction and validation of ash sticking probability under fouling conditions in pulverized coal combustion

Under the fouling conditions in stationary coal combustion systems, the sticking/rebound behavior of solid incident particles is a key issue in determining the ash deposition rate. From a dynamic point of view, the bulk fly ash, which dominants the deposited mass, successively interacts with the clean tube, the inner fine deposited layer and the bulk deposited layer during ash deposition. In this paper, we experimentally investigate the time-resolved evolution of ash fouling in a 25 kW coal combustor. The deposited mass flux rapidly reaches a stable state that fluctuates around a mean value of ～3 g/(m²·s) for two kind of probe materials. The rapid initial stage only allows the formation of 1–2 layers of bulk deposited ash, revealing the dominant role of bulk deposit in capturing large incident particles. Inspired by the observation, we apply a 3D adhesive discrete element model (DEM) to fully describe the many-body evolving process subject to the incident events of a 30-µm particle. The simulation agrees well with the experiments when using a higher particle surface energy of 200 mJ/m². The rapidly growing feature of ash sticking probability with increasing the bulk deposit layers can be reproduced in this case, and an empirical formula is proposed. It is also validated that, at the deposit growth stage, the newly-deposited particles stay just where they impact. The effectiveness of the DEM tool shall benefit a fully-validated sticking/rebound model under the fouling condition that is convenient for CFD use.     

Effect of pyrolysis conditions on the char gasification with mixtures of CO2 and H2O

Two kinds of char were prepared from a lignite by fast pyrolysis using a drop tube furnace and by slow pyrolysis using a fixed-bed furnace at the temperature of 1273 K. Scanning electron microscopy, X-ray diffractometry and the BET method were employed to characterize char properties. The chars were gasified with CO₂, H₂O and their mixtures in a thermogravimetric analyzer (TGA) system to investigate gasification kinetics and derive the rate expression. To validate the gasification rate equation derived from TGA, a fluidized-bed gasification experiment was also carried out. The results showed that both fast-char and slow-char were mainly composed of dense char. The shrinking core model was applicable to predict both gasification of fast-char and slow-char. It was found that the char gasification rate in the mixtures of CO₂ and H₂O was obviously lower than the sum of the two rates of the char independently reacting with CO₂ and H₂O but higher than the rate of each independent reaction, for both the fast-char gasification and slow-char gasification. Both of the results from the TGA and the fluidized-bed reactor showed that char-H₂O reaction was independent on char-CO₂ reaction, while char-CO₂ reaction was inhibited by char-H₂O reaction.     

The effect of pelletization on the attrition of wood under fluidized bed combustion and gasification conditions

This work reports on a study, carried out in a lab-scale fluidized bed apparatus, on fragmentation and attrition of two biomass fuels, namely wood chips and wood pellets, under both combustion and gasification conditions. The aim was to highlight the effect of their different mechanical strength on the fuel particle size distribution and overall carbon conversion. Primary fragmentation tests showed that for wood pellets limited fragmentation occurred during devolatilization, with a fragmentation probability around 30% and particle multiplication factor of 1.4. On the contrary, wood chips were subject to extensive fragmentation as witnessed by large values of the particle multiplication factor and of the fragmentation probability.Results of char attrition experiments carried out under inert, combustion and gasification conditions showed that the carbon loss by elutriation is critical only during gasification, especially for the wood chips char. A gasification-assisted attrition mechanism was proposed to explain the experimental results, similar to the well known combustion-assisted attrition patterns already documented for coal under oxidizing conditions. The higher mechanical strength of the wood pellets appears to be beneficial for reducing carbon elutriation and for obtaining a higher carbon conversion.     

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.     

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.     

The role of porosity in char combustion

A detailed study has been conducted on the nature of porosity developed during the combustion of chars prepared from different coals, and how this relates to the apparent reactivity of the char towards oxygen. An Illinois No. 6 coal char and a Wyodak coal char have been examined in both Zone I and Zone II conditions (intrinsic rate control and diffusional mass transfer zones, respectively). These results strongly suggest that there exists some amount of free volume in a char that has not been burned off. Such an unburned char does not reveal much porosity when standard nitrogen adsorption is applied, but rapidly develops such porosity upon burnoff. The free volume opens, but is not truly accessible to reactant gases. It appears likely, based upon the present results, that the only truly available surface for reaction exists in pores larger than 10–15 Å.     

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.