Effect of reactivity loss on apparent reaction order of burning char particles

Considerable debate still exists in the char combustion community over the expected and observed reaction orders of carbon reacting with oxygen. In particular, very low values of the reaction order (approaching zero) are commonly observed in char combustion experiments. These observations appear to conflict with porous catalyst theory as first expressed by Thiele, which suggests that the apparent reaction order must be greater than 0.5. In this work, we propose that this conflict may be resolved by considering the decrease in char reactivity with burnout due to ash effects, thermal annealing, or other phenomena. Specifically, the influence of ash dilution of the available surface area on the apparent reaction order is explored. Equations describing the ash dilution effect are combined with a model for particle burnout based on single-film nth-order Arrhenius char combustion and yield an analytical expression for the effective reaction order. When this expression is applied for experimental conditions reflecting combustion of individual pulverized coal particles in an entrained flow reactor, the apparent reaction order is shown to be lower than the inherent char matrix reaction order, even for negligible extents of char conversion. As char conversion proceeds and approaches completion, the apparent reaction order drops precipitously past zero to negative values. Conversely, the inclusion of the ash dilution model has little effect on the char conversion profile or char particle temperature until significant burnout has occurred. Taken together, these results suggest that the common experimental observation of low apparent reaction orders during char combustion is a consequence of the lack of explicit modeling of the decrease in char reactivity with burnout.     

Combustion kinetics of coal chars in oxygen-enriched environments

Oxygen-enhanced and oxygen-fired pulverized coal combustion is actively being investigated to achieve emission reductions and reductions in flue gas cleanup costs, as well as for coal-bed methane and enhanced oil recovery applications. To fully understand the results of pilot scale tests and to accurately predict scale-up performance through CFD modeling, accurate rate expressions are needed to describe coal char combustion under these unconventional combustion conditions. In the work reported here, the combustion rates of two pulverized coal chars have been measured in both conventional and oxygen-enriched atmospheres. A combustion-driven entrained flow reactor equipped with an optical particle-sizing pyrometry diagnostic and a rapid-quench sampling probe has been used for this investigation. Highvale subbituminous coal and a high-volatile eastern United States bituminous coal have been investigated, over oxygen concentrations ranging from 6 to 36 mol% and gas temperatures of 1320-1800 K. The results from these experiments demonstrate that pulverized coal char particles burn under increasing kinetic control in elevated oxygen environments, despite their higher burning rates in these environments. Empirical fits to the data have been successfully performed over the entire range of oxygen concentrations using a single-film oxidation model. Both a simple nth-order Arrhenius expression and an nth-order Langmuir-Hinshelwood kinetic equation provide good fits to the data. Local fits of the nth-order Arrhenius expression to the oxygen-enriched and oxygen-depleted data produce lower residuals in comparison to fits of the entire dataset. These fits demonstrate that the apparent reaction order varies from 0.1 under near-diffusion-limit oxygen-depleted conditions to 0.5 under oxygen-enriched conditions. Burnout predictions show good agreement with measurements. Predicted char particle temperatures tend to be low for combustion in oxygen-depleted environments.     

Kinetics of devolatilization and oxidation of a pulverized biomass in an entrained flow reactor under realistic combustion conditions

In this paper the results of a complete set of devolatilization and combustion experiments performed with pulverized (∼500 μm) biomass in an entrained flow reactor under realistic combustion conditions are presented. The data obtained are used to derive the kinetic parameters that best fit the observed behaviors, according to a simple model of particle combustion (one-step devolatilization, apparent oxidation kinetics, thermally thin particles). The model is found to adequately reproduce the experimental trends regarding both volatile release and char oxidation rates for the range of particle sizes and combustion conditions explored. The experimental and numerical procedures, similar to those recently proposed for the combustion of pulverized coal [J. Ballester, S. Jiménez, Combust. Flame 142 (2005) 210-222], have been designed to derive the parameters required for the analysis of biomass combustion in practical pulverized fuel configurations and allow a reliable characterization of any finely pulverized biomass. Additionally, the results of a limited study on the release rate of nitrogen from the biomass particle along combustion are shown.     

Effect of CO2 and steam gasification reactions on the oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, elevated levels of CO₂ and steam affect the heat capacity of the gas, radiant transport, and other gas transport properties. A topic of widespread speculation has concerned the effect of gasification reactions of coal char on the char burning rate. To asses the impact of these reactions on the oxy-fuel combustion of pulverized coal char, we computed the char consumption characteristics for a range of CO₂ and H₂O reaction rate coefficients for a 100 μm coal char particle reacting in environments of varying O₂, H₂O, and CO₂ concentrations using the kinetics code SKIPPY (Surface Kinetics in Porous Particles). Results indicate that gasification reactions reduce the char particle temperature significantly (because of the reaction endothermicity) and thereby reduce the rate of char oxidation and the radiant emission from burning char particles. However, the overall effect of the combined steam and CO₂ gasification reactions is to increase the carbon consumption rate by approximately 10% in typical oxy-fuel combustion environments. The gasification reactions have a greater influence on char combustion in oxygen-enriched environments, due to the higher char combustion temperature under these conditions. In addition, the gasification reactions have increasing influence as the gas temperature increases (for a given O₂ concentration) and as the particle size increases. Gasification reactions account for roughly 20% of the carbon consumption in low oxygen conditions, and for about 30% under oxygen-enriched conditions. An increase in the carbon consumption rate and a decrease in particle temperature are also evident under conventional air-blown combustion conditions when the gasification reactions are included in the model.     

炉内煤粉燃烧一维数学模型及其仿真

为了准确计算炉内煤粉的燃尽率,从研究煤粉粒子的燃烧机理入手,以炉膛内最复杂的燃烧器区域的煤粉燃烧过程为研究对象,通过合理简化煤粉中挥发分和焦炭的燃烧过程,建立了炉内煤粉燃烧沿高度方向上的一维宏观模型,在模型中考虑了煤粉燃烧过程中氧含量的变化,以单个煤粉颗粒燃烧的等密度模型为基础,通过多种煤粉粒径的燃烧过程反映煤粉燃烧的整体过程,推导出计算炉内煤粉燃尽率的显示公式,满足了实时仿真计算的要求。计算结果与实测数据和现有的文献相符,并对结果进行了分析。     

A model of coal devolatilization and combustion in fluidized beds

A mathematical model of the combustion of coal particles under conditions prevailing in fluidized combustors has been developed. Allowance is made for the evolution and burning of volatiles in addition to the combustion of the residual char. The relative significance of the various steps in the oxidation process of the char, such as external diffusion, pore diffusion, and chemical kinetics of the reactions at the surface, is evaluated for the ranges of particle size, temperature, and partial pressure of the oxidant of interest in fluidized coal combustion.     

Modeling char oxidation behavior under Zone II burning conditions at elevated pressures

For accurate modeling of the coal combustion process at elevated pressures, account must be made for variations in char-particle structure. As pressure is increased, particle swelling increases during the devolatilization of certain bituminous coals, yielding a variety of char-particle structures, from uniform high-density particles to thin-walled non-uniform low-density particles having large internal void volumes. Since under Zone II burning conditions the char conversion rate depends upon the accessibility of the internal surfaces, the char structure plays a key role in determining particle burnout times. In our approach to characterize the impact of char structure on particle burning rates, effectiveness factors appropriate for thin-walled cenospherical particles and thick-walled particles having a few large cavities are defined and related to the effectiveness factor for uniform high-density particles that have no large voids, only a random distribution of pores having a mean pore size in the sub-micron range. For the uniform case, the Thiele modulus approach is used to account for Zone II type burning in which internal burning is limited by the combined effects of pore diffusion and the intrinsic chemical reactivity of the carbonaceous material. In the paper, the impact of having a variety of char structures in a mix of particles burning under Zone II burning conditions is demonstrated.     

Analysis and modeling of char particle combustion with heat and multicomponent mass transfer

A char combustion model suitable for a large-scale boiler/gasifier simulation, which considers the variation of physical quantities in the radial direction of char particles, is developed and examined. The structural evolution within particles is formulated using the basic concept of the random pore model while simultaneously considering particle shrinkage. To reduce the computational cost, a new approximate analytical boundary condition is applied to the particle surface, which is approximately derived from the Stefan–Maxwell equations. The boundary condition showed reasonably good agreement with direct numerical integration with a fine grid resolution by the finite difference method under arbitrary conditions. The model was applied to combustion in a drop tube furnace and showed qualitatively good agreement with experiments, including for the burnout behavior in the late stages. It is revealed that the profiles of the oxygen mole fraction, conversion, and combustion rate have considerably different characteristics in small and large particles. This means that a model that considers one total conversion for each particle is insufficient to describe the state of particles. Since our char combustion model requires only one fitting parameter, which is determined from information on the internal geometry of char particles, it is useful for performing numerical simulations.     

旋风炉内气相燃烧及两相流动的数值模拟

在有反应两相流动及煤粉燃烧的全双流体模型（ＰＴＦ模型,ｐｕｒｅ ｔｗｏ－ｆｌｕｉｄ ｍｏｄｅｌ）基础上,采用修正的ｋ－ε－ｋｐ两相湍流模型,对旋风炉内的湍流气相燃烧（甲烷和一氧化碳的燃烧）及在气相燃烧条件下的两相流动进行了数值模拟研究,模拟结果表明,在有燃烧的情况下,在旋风炉的底部存在近壁回流区,该回流区有利于火焰稳定,气粒两相切向速度分布具有类似的Ｒａｎｋｉｎｅ涡结构,该研究为煤粉燃烧的数值模拟     

煤粉炉燃烧效率工程预测模型

整理了前人有关煤焦燃烧反应的动力学数据，在此基础上，建立了适合于工程计算的煤粉炉燃烧效率预测模型。该模型能够定量分析煤种、煤粉细度、运行氧量、炉膛温度、燃尽高度等多种参数对燃烧效率的影响。采用该模型对实际运行锅炉的计算表明，它能够较为准确地预测飞灰未燃尽碳含量，可以用于煤粉锅炉燃烧效率预报分析，为选择合适的设计和运行参数提供指导。图6表3参3。     

Coke generation and conversion behavior of pulverized coal combustion

Preheating combustion is a promising novel low-nitrogen technology. The coke generation and conversion behavior in the preheater and combustion chamber are studied in this paper. The particle size distribution, apparent morphology, specific surface area, pore structure distribution and combustion reactivity of the coke can be analyzed respectively with the particle size analyzer, scanning electron microscope, automatic specific surface area analyzer and Raman spectrometer. The results show that the preheated char generated by the preheating process has some merits: the particle size is smaller, specific surface area is larger, the pore structure is more developed and combustion reactivity is higher. In the down-fired combustor, the degree of particle breakage, apparent morphology, specific surface area and pore structure are influenced by the combustion reaction intensity. Combining the analysis of the graphite stable structure and the active carbon defect structure, the combustion reactivity order of four samples is: 100 mm  >  400 mm > preheated char> 900 mm. This paper provides experimental support and theoretical analysis for this technology to achieve deep control of nitrogen.     

Gasification of a pulverized sub-bituminous coal in CO2 at atmospheric pressure in an entrained flow reactor

Char gasification by CO₂ may play an important role in oxy-fuel applications and affect particle temperature histories and overall reaction rates during combustion. This paper presents the results of a complete set of experiments of char gasification in CO₂ performed with a pulverized Indonesian sub-bituminous coal in an entrained flow reactor under realistic conditions; series of burnout curves at different reactor temperatures (1040–1300 °C) and CO₂ concentrations (0.7–100%) reveal consistent trends in the gasification rates. The study included also devolatilization and oxidation tests with this coal in the same experimental facility. The data are used to derive apparent kinetics for the three processes, in a manner similar to that followed in a previous work for the oxidation of a pulverized coal. The gasification kinetic parameters and reaction rates measured are then compared with values taken or derived from previous works by others, obtained by thermogravimetric analysis or experiments in entrained flow reactors. Finally, the relevance of char gasification in the overall reaction rate under conditions representative of those in an industrial boiler is explored, in particular for the case of oxy-coal combustion.     

The conversion mode of a porous carbon particle during oxidation and gasification

Studies have shown that both char particle diameter and apparent density vary during char conversion at high temperatures. To account for such variations, power-law expressions have been used to correlate r_p/r_p,0 and ρ_p/ρ_p,0 with m_p/m_p,0. The parameters in these relations are constants, thus this approach fails to account for variations in the functional relationship between mass, size, and apparent density as mass conversion proceeds. To overcome this limitation, a model for the mode of particle conversion has been developed that permits the variation in size and apparent density with mass loss to depend upon the Thiele modulus, which varies during char conversion. The rate with which the particle radius decreases is shown to be given by the ratio of the time derivative and the spatial derivative of the particle density at the surface of the particle. The model presented can be used to describe the mode of conversion of reactive porous particles in a range of different applications such as entrained flow gasifiers, pulverized coal burners and circulating fluidized bed combustors. There are no free tunable parameters in the model.     

Experimental investigation of the two-phase theory in a fluidized-bed combustor

Though the two-phase theory of fluidization is well-accepted, no direct experimental measurements of the different gas concentrations predicted to occur in bubble and particulate phases could be found in the literature. For the first time, theoretical predictions of these different gas concentrations have been validated experimentally, using a combined oxygen/bubble probe. Based on the two-phase theory, a mathematical model was developed for the combustion of a batch of char particles in a fluidized-bed combustor. The experimental oxygen concentration in the particulate phase as a function of time was well predicted by the model. Slight discrepancies for the bubble phase values were eliminated when low-oxygen-concentration bubbles were excluded from the data, attributed to some char combustion occurring in bubbles being contrary to the model assumption. The temperature difference between char and bed particles (ΔT) was the only adjustable parameter in the model. A value of 20°C fitted the burnoff times measured by visual observation of the top of the bed, for both 5 and 10 g char batch masses. Model predictions of the oxygen concentrations were not sensitive to ΔT during the first half of burnoff, when mass transfer controlled the combustion rate, so the mass transfer processes were predicted correctly by the model effectively with no adjustable parameter. The ΔT value of 20°C was significantly lower than experimental measurements of maximum burning char particle temperatures, reported to be 70°C for the small-diameter bed particles used in this work. The discrepancy was attributed to two factors: (i) the decrease in char particle temperature towards the end of the burnoff, when kinetics significantly affected the combustion rate; and (ii) a lower char particle temperature in the particulate phase than in the bubble phase, with experimental char particle temperature measurements biased towards the higher bubble phase values. It was inferred: (i) that the maximum values of ΔT measured experimentally are too high for calculation of the char particle combustion rate during the kinetic-controlled latter stage of burnoff and (ii) that reported values of the heat transfer coefficient from burning char particles to the particulate phase deduced from these particle temperature measurements may have been underestimated.     

Study of the evolution of particle size distributions and its effects on the oxidation of pulverized coal

This paper discusses the factors influencing the evolution of particle size during the combustion of pulverized coal, as well as their consequences for the interpretation of burnout curves. A detailed experimental characterization of the evolution of the particle size distribution (PSD) of a pulverized coal (anthracite) burned under realistic conditions in an entrained flow reactor is presented and used as the reference data for the subsequent analysis. The data show evidence for particle fragmentation at relatively short times (or, equivalently, high unburnt fractions). The formation of fragments comparable in size to the parent coal/char particles is modeled with a simple fragmentation scheme, which results in an improved reproduction of the PSD's evolution. The effects of fragmentation on the burnout curves are then studied in detail. An enhancement of their curvature is observed, which results in a better fit of the experimental data; in particular, the high conversion range, where the largest discrepancies between predictions and measurements are usually found, is well reproduced with this “extended” model. Simultaneously, the increase of specific surface caused by particle fragmentation causes an increase in the conversion rate, and a smaller total conversion time. To fit the experimental data, new optimal kinetic parameters are calculated. Finally, the potential relevance of fragmentation in the simulation of industrial pf plants is discussed.     

Multivariable optimization of reaction order and kinetic parameters for high temperature oxidation of 10 bituminous coal chars

In industrial pulverized fuel combustion, char oxidation is generally limited by the combined effects of chemical reactions and pore diffusion. Under such conditions, char oxidation is frequently predicted by power law models, which despite their simplicity, are widely used in the comprehensive CFD modeling of pulverized coal boilers. However, there is no consensus on the apparent reaction order given by such models. This study developed a systematic approach which gives consistent values over a range of conditions. Apparent reaction orders for 10 bituminous coal chars were investigated with three different oxygen concentrations, ranging from 4 to 12 vol.%, and a gas temperature of 1223 K for each char. Experimental burnout profiles of the chars were obtained by means of an Isothermal Plug Flow Reactor operating at industrially realistic heating rates (10⁴ K/s). For various reaction orders between 0.05 and 2.00, kinetic parameters were independently determined, following numerical procedures recently suggested in the literature. The resulting values were incorporated into an empirical power law model and compared to experimental data for the 10 chars, over a burnout range of 0–75%. The best fit to the experiments occurs with apparent reaction orders of around one for all the chars.     

Continuous lignite char combustion in a spouted bed

A simulation model of continuous lignite char combustion in a spouted bed has been developed to predict bed oxygen concentrations, bed particle size distribution, bed carbon loading, mean diameter of bed char, and the fractional combustion in spout, annulus, and fountain. The approach involves taking into account the spouted bed hydrodynamics, a burning law for individual particles, and the combines mass balances for bed char and oxidant in the three typical regions. The predicted results for various operating conditions are compared with some experimental data.     

Numerical Studies on Combustion Characteristics of Interacting Pulverized Coal Particles at Various Oxygen Concentration

The two-dimensional laminar combustion characteristics of coal particles at various oxygen concentration levels of a surrounding gas have been numerically investigated. The numerical simulations, which use the two-step global reaction model to account for the surrounding gas effect, show the detailed interaction among the inter-spaced particles, undergoing devolatilization and subsequent char burning. Several parametric studies, which include the effects of gas temperature (1700 K), oxygen concentration, and variation in geometrical arrangement of the particles on the volatile release rate and the char burning rate, have been carried out. To address the change in the geometrical arrangement effect, multiple particles are located at various inter-spacings of 4–20 particle radii in both streamwise and spanwise directions. The results for the case of multiple particles are compared with those for the case of a single particle. The comparison indicates that the shift to the multiple particle arrangement resulted in the substantial change of the combustion characteristics and that the volatile release rate of the interacting coal particles exhibits a strong dependency on the particle spacing. The char combustion rate is controlled by the level of oxygen concentration and gas composition near particles during combustion. The char combustion rate is highly dependent on the particle spacing at all oxygen levels. The correlations of the volatile release rate and the change in total mass of particles are also found.     

挥发分火焰对碳粒燃烧的影响

建立了球坐标系下传热、传质、化学反应全耦合的煤粉燃烧数值模拟程序．通过煤粉与事先脱除挥发分的焦炭的对比实验及数值模拟,研究了挥发分火焰对碳粒表面一次产物CO火焰的点燃及碳粒燃烧的影响．傅里叶变换红外光谱仪(FTIR)测温实验及煤粉燃烧动态过程的数值模拟结果不仅进一步验证了碳粒着火初期CO火焰所引起的颗粒高温现象,而且给出了挥发分引燃表面反应一次产物CO的直接证据．由于挥发分火焰的引燃作用,碳粒可以在较其非均相着火温度为低的温度下被点燃,阐明了Juntgen提出的联合着火方式的物理本质．