Fluidized combustion of char and volatiles from coal

This paper reviews the literature about fluidized combustion of char and volatiles from coal. While the rate of combustion of particles bigger than about 2 mm is mainly limited by the rate of diffusion of oxygen, there is usually an effect of chemical rate. As particle diameter decreases, the influence of chemical rate increases. Char particles are porous and combustion occurs in pores near their exterior. Char reactivity can be modelled by an effective pore area for combustion. At high bed temperatures (>1,150 K), the rate of combustion of volatiles is limited by the rate of mixing of fuel and oxygen. At low bed temperatures (<1,000 K), combustion reactions are inhibited by the inert particles in the bed.     

Modeling the temperature in coal char particle during fluidized bed combustion

The temperatures of a coal char particle in hot bubbling fluidized bed (FB) were analyzed by a model of combustion. The unsteady model includes phenomena of heat and mass transfer through a porous char particle, as well as heterogeneous reaction at the interior char surface and homogeneous reaction in the pores. The parametric analysis of the model has shown that above 550 °C combustion occurs under the regime limited by diffusion. The experimental results of temperature measurements by thermocouple in the particle center during FB combustion at temperatures in the range 590-710 °C were compared with the model predictions. Two coals of different rank were used: lignite and brown coal, with particle size in the range 5-10 mm. The comparisons have shown that the model can adequately predict the histories of temperatures in char particles during combustion in FB. In the first order, the model predicts the influence of the particle size, coal rank (via porosity), and oxygen concentration in its surroundings.     

Internal burning of petroleum coke particles in a fluidized bed

Physical properties of small irregular petroleum coke particles (3.08 mm) have been measured at various stages of combustion in a fluidized bed of sand operating in the range 973–1173 K. Internal burning took place during the particle heating period even at bed temperatures of 1173 K. However, at this temperature, the particles burnt predominantly under mass transfer control subsequent to ignition and particle heating. Combustion behaviour at 973 K was typical of internal burning characteristics, i.e. pore enlargement and decrease in particle density continued as burning progressed.     

In-bed char combustion of Australian coals in PFBC. 2. Char combustion without secondary fragmentation

Char combustion parameters that significantly affect the in-bed combustion of char in PFBC were determined experimentally using a batch-fed PFBC. The ratio of carbon to oxygen consumed on the surface of a burning char particle was determined and it was concluded that CO was the only product of char combustion in PFBC.

Model simulations revealed that, for PFBC, mass transfer controlled the combustion of large char particles ≥2 mm, whereas the combustion of small char particles below 0.9–2 mm was controlled by both mass transfer and chemical kinetics.

System pressure influenced the char combustion via the interaction between chemical kinetics and the mass transfer of oxygen to the char. Char particle temperature varied markedly with oxygen partial pressure in the particulate phase, indicating a distribution of char particle combustion rates in PFBC. In modelling char combustion in PFBC, the temperature of char particles in the bed should be calculated at different locations based on a heat balance around the burning char particle taking into account the local bed oxygen concentration.     

Analysis of cyclic combustion of solid fuels

The cyclic nature of coal particles combustion results from the movement of loose material in the flow contour of the circulating fluidized bed (CFB): the combustion chamber, the cyclone, the downcomer.The experimental results proved that the cyclic change of the oxygen concentration around coal particles, led to the vital change of both mechanism and combustion kinetics. The mathematical model of the process of coal combustion has been scientifically described whose original concept is based on the allowance for cyclic changes of concentrations of oxygen around the char particle. It enables the prognosis for change of the surface and the centre temperatures and a mass loss of the char particles during the cyclic combustion. It allows to appoint mass-rate of combustion of a char particle in the above conditions.     

典型尺寸燃煤颗粒富氧燃烧特性及燃烧本征动力学研究

利用微型流化床加热速度快、温度分布均匀以及气体近平推流等优势,在直径20 mm自动控温的微型流化床反应分析仪中研究了粒度分布为1.7～3.35 mm和0.12～0.23 mm两种典型尺寸燃煤颗粒在790～900℃温度范围内的富氧燃烧行为。通过快速响应过程质谱对燃烧产生的烟气进行实时监测,成功地识别和记录了粗颗粒燃烧过程中经历的挥发分燃烧和原位新生半焦燃烧两个主要阶段。挥发分析出速度最快,然后快速燃烧,而半焦燃烧速度较慢。相比之下,细颗粒燃烧的这两个阶段具有几乎相同的速率,因而相互耦合而难以区分。根据实验结果,挥发分析出和燃烧为快速反应,煤颗粒燃烧过程速率受原位新生半焦燃烧过程控制。进一步研究了挥发分和原位新生半焦燃烧动力学行为,获得其本征动力学的活化能分别为107.2和143.9 kJ/mol。     

海藻生物质颗粒流化床燃烧试验研究

在小型流化床试验台上研究了海藻颗粒(条浒苔与马尾藻)的流化床燃烧。海藻在流化床内的挥发分析出燃烧时间都在1 min左右。条浒苔颗粒在流化床中燃烧先进行脱水和挥发分的燃烧,接着发生焦炭燃烧,其燃烧过程符合缩核模型,炭核由外向内逐层燃烧,而灰层半径几乎不变。但马尾藻颗粒由于挥发分的大量快速释放而迅速膨胀破碎成屑。另外通过对条浒苔颗粒及不同燃烧时间后收集的焦炭颗粒剖面的SEM扫描电镜观察,发现随着燃烧的进行,颗粒内孔隙增大,微孔表面粗糙。进一步详细研究了两种海藻颗粒(条浒苔与马尾藻)在流化床内单次投料下的燃烧。随着床温的升高,条浒苔释放NO_x相对浓度增加,CO相对浓度减少。而马尾藻释放气体中SO₂与NO_x含量相对条浒苔有所增加;随着床温的升高,CO相对浓度减少。床温的升高使得床内传热速率加快,两种海藻挥发分的析出提前,燃尽时间缩短。风速、床高的升高使得两种海藻燃烧容易,燃尽时间缩短。     

An extended DEM–CFD model for char combustion in a bubbling fluidized bed combustor of inert sand

This paper proposes a transient three-phase numerical model for the simulation of multiphase flow, heat and mass transfer and combustion in a bubbling fluidized bed of inert sand. The gas phase is treated as a continuum and solved using the computational fluid dynamics (CFD) approach; the solid particles are treated as two discrete phases with different reactivity characteristics and solved on the individual particle scale using an extended discrete element model (DEM). A new char combustion submodel considering sand inhibitory effects is also developed to describe char particle combustion behavior in the fluidized bed. Two conditions, i.e. a single larger graphite particle and a batch of smaller graphite particles, are used to test the prediction capability of the model. The model is validated by comparing the predicted results with the previous measured results and conclusions in the literature in terms of bed hydrodynamics, individual particle temperature, char residence time and concentrations of the products. The effects of bed temperature, oxygen concentration and superficial velocity on char combustion behavior are also examined through model simulation. The results indicate that the proposed model provides a proximal approach to elucidate multiphase flow and combustion mechanisms in fluidized bed combustors.     

Model for biomass char combustion in the riser of a dual fluidized bed gasification unit: Part II — Model validation and parameter variation

The two-phase combustion model for biomass char combustion in a riser of a dual fluidized bed gasification unit that has been presented in part I is validated using the data obtained from the 8 MWth dual fluidized bed reactor at Guessing/Austria. The model is capable of calculating the average temperatures in all zones, the gas phase composition, solid hold up, char feed rates and air ratio. The model predictions for the temperature profile along the riser and for the exiting gas composition are in good agreement with the measured values. The simulation results show that the residual char from the gasifier is only partly converted in the riser for char particles larger than 0.6 mm. Un-combusted char is circulated back into the gasification reactor. Parameter variations show that the exact location where additional liquid fuels are introduced in the middle zone of the riser does not affect the global behaviour of the combustion reactor. Based on the simulation results it is proposed that external supply of char (additional) may be a very effective method for reducing producer gas recycling to the riser, which is currently necessary to obtain the desired gasification temperatures.     

Modelling of circulating fluidized bed combustion of a char

The combustion of a char in the 41 mm ID riser of a laboratory circulating fluidized bed combustor has been investigated at different air excesses and rates of solids (char and sand) circulating in the loop. Riser performance was characterized by an axial oxygen concentration profile as well as by the overall carbon content and particle size distribution. The proposed model accounts for carbon surface reaction, intraparticle and external diffusion, and attrition. External diffusion effects were relevant in the riser dense region where char was potentially entrapped in large clusters of inert solids. Experimental data and results of the model calculations are in satisfactory agreement.     

CARBON COMBUSTION RATES AND TEMPERATURES IN SHALLOW FLUIDIZED BEDS

The mechanism of combustion of carbon in shallow fluidized beds at temperatures 750-1000°C is studied by measuring burning rates and temperatures of spherical carbon particles ranging from 2 mm to 12 mm diameter directly in an experimental fluidized bed. Among variables investigated were inert particle size, superficial fluidizing velocity, temperature, the influence of neighbouring active particles and oxygen concentration in the fluidizing gas.

Under the experimental conditions explored, combustion was mainly kinetically controlled, so that with carbon particles larger than about 4 mm, burning rates are significantly higher than those predicted by combustion models which assume combustion to be controlled by the rate at which oxygen diffuses through a stagnant particulate phase surrounding the burning particle. The higher burning rate seems to arise because the greater mobility of particles in the bed causes the restriction to oxygen flow to the carbon surface offered by the particulate phase to be reduced and has important consequences for combustor design.

Measured carbon particle temperatures were influenced considerably by bed operating conditions ranging from 15 to 215°C higher than bed temperature.

Measured burning rates of carbon particles were found to be reduced significantly when other active particles were present in the bed. This sensitivity of burning rate to changes in active particle concentration in the bed was shown to be increasingly important once the concentration of carbon in the bed exceeded about 1%

Increasing the bed inert particle size, superficial fluidizing velocity, oxygen concentration in the fluidizing gas and bed temperature resulted in higher burning rates. The implication of these findings on combustor design are discussed.     

Modelling and experimental validation of a fluidized-bed reactor freeboard region: Application to natural gas combustion

A theoretical and experimental study of natural gas–air mixture combustion in a fluidized bed of sand particles is presented. The operating temperatures are lower than a critical temperature of 800 °C above which the combustion occurs in the vicinity of the fluidized bed. Our study focusses on the freeboard zone where most of the methane combustion takes place at such temperatures. Experimental results show the essential role of the projection zone in determining the global thermal efficiency of the reactor. The dense bed temperature, the fluidizing velocity and the mean particle diameter significantly affect the thermal behaviours.A model for natural gas–air mixture combustion in fluidized beds is proposed, counting for interactions between dense and dilute regions of the reactor [P. Pré, M. Hemati, B. Marchand, Study of natural gas combustion in fluidised beds: modelling and experimental validation, Chem. Eng. Sci. 53 (1998) (16), 2871] supplemented with the freeboard region modelling of Kunii–Levenspiel [D. Kunii, O. Levenspiel, Fluidized reactor models: 1. For bubbling beds of fines, intermediate and large particles. 2. For the lean phase: freeboard and fast fluidization, Ind. Eng. Chem. Res. 29 (1990) 1226–1234]. Thermal exchanges due to the convection between gas and particles, and due to the conduction and radiation phenomena between the gas-particle suspension and the reactor walls are counted. The kinetic scheme for the methane conversion is that proposed by Dryer and Glassman [F.L. Dryer, I. Glassman, High-temperature oxidation of CO and CH₄, Proceedings of the 14th International Symposium on Combustion, The Combustion Institute, Pittsburg (1973) 987]. Model predictions are in good agreement with the measurements.     

Studies in char gasification—I A lumped model

The gasification of char in a steam-oxygen fluidized bed was studied. The char was assumed to be composed of base carbon and ash. The gaseous compounds found were limited to CO, CO₂, H₂, H₂O, O₂ and CH₄. As the oxygen and hydrogen were assumed not to co-exist, the bed was divided into a shallow combustion zone where the carbon combustion would take place and a gasification zone where no oxygen would be found. A lumped model for the gasification zone was formulated. The thickness of the combustion zone was assumed to be negligible compared to the total height of the reactor. All chemical changes in the gasification zone were described by three reactions: steam gasification, carbon hydrogasification and water-gas shift reaction. The gases and the solids in the gasification zone were assumed to be at uniform temperature. From the results of the model calculations it was concluded that one should use the fairly complicated empirical kinetic expressions developed by Johnson for reliability over a wide range of pressures and residence times. The effects of the reactor pressure, the char residence time and the amount of oxygen in the feed on the gasifier performance were analysed.     

CARBON COMBUSTION RATES AND TEMPERATURES IN SHALLOW FLUIDIZED BEDS

Abstract

The mechanism of combustion of carbon in shallow fluidized beds at temperatures 750-1000°C is studied by measuring burning rates and temperatures of spherical carbon particles ranging from 2 mm to 12 mm diameter directly in an experimental fluidized bed. Among variables investigated were inert particle size, superficial fluidizing velocity, temperature, the influence of neighbouring active particles and oxygen concentration in the fluidizing gas.

Under the experimental conditions explored, combustion was mainly kinetically controlled, so that with carbon particles larger than about 4 mm, burning rates are significantly higher than those predicted by combustion models which assume combustion to be controlled by the rate at which oxygen diffuses through a stagnant particulate phase surrounding the burning particle. The higher burning rate seems to arise because the greater mobility of particles in the bed causes the restriction to oxygen flow to the carbon surface offered by the particulate phase to be reduced and has important consequences for combustor design.

Measured carbon particle temperatures were influenced considerably by bed operating conditions ranging from 15 to 215°C higher than bed temperature.

Measured burning rates of carbon particles were found to be reduced significantly when other active particles were present in the bed. This sensitivity of burning rate to changes in active particle concentration in the bed was shown to be increasingly important once the concentration of carbon in the bed exceeded about 1%

Increasing the bed inert particle size, superficial fluidizing velocity, oxygen concentration in the fluidizing gas and bed temperature resulted in higher burning rates. The implication of these findings on combustor design are discussed.     

The kinetics of combustion of chars derived from sewage sludge

Experiments have been conducted to determine the combustion characteristics of sewage sludge chars in electrically heated beds of silica sand fluidised by air. The effects of the initial size of the char particles, the temperature of the bed and [O₂] in the fluidising gas were investigated. Also, the temperatures of burning particles were measured with embedded thermocouples. The kinetics of combustion were measured at temperatures low enough for the CO formed by initial reaction between the carbon and oxygen to burn at some distance away from the particle. Accordingly, the particle is only heated by the enthalpy of the reaction C+0.5O₂→CO. The activation energy for the intrinsic kinetics of combustion of the char was estimated to be 130–144 kJ/mol. The former value makes allowance for the fact that the particles are at a temperature in excess of that of the bed (determined by a heat balance on a reacting particle), whilst the latter value assumes that the particles are at the same temperature of the bed. It is probable that the lower value is closer to the actual value, thought to be 135±15 kJ/mol, reflecting the catalytic nature of the ash skeleton on which the carbon is supported. It was possible to obtain good agreement between measured burnout times and those predicted using the grain model of Szekely J, Evans JW, Sohn HY. Gas–solid reactions. New York: Academic Press; 1976, for the case where the kinetics are controlled by a combination of: (i) external mass transfer of oxygen from the particulate phase to the external surface of the burning char particle, (ii) diffusion of oxygen from the external surface into the porous matrix to the surfaces of grains, of which the solid is composed, and (iii) diffusion of oxygen into the microporous grains, where reaction occurs with the carbon. It was found that, for particles with diameters of 2 mm or larger, the initial rates of reaction, for bed temperatures in excess of 750 °C, are dominated by external mass transfer. This explains the dependence of the rate of oxidation of unit mass of char on 1/d_p, and the relatively small influence of temperature on these rates. Particles of char from sewage sludge are so reactive that it is essential to make allowance for a difference in temperature between the particle and the bed. Thus, experimental determinations on particles with d_p∼6.5 mm, suggested a difference in temperature of ∼150 K, in line with calculations using a steady-state heat balance.     

Fluidized bed combustion of wet brown coal

The behaviour of very wet Victorian brown coal was examined in a bed of sand fluidized, at temperatures around 1000 K, with either air or nitrogen. Small batches of coal with a narrow particle size range were added to the 76 mm diameter bed and the times required for devolatilization and total combustion were recorded. Changes in particle water content, volatiles level and particle size distribution were also measured. All the particles tested, up to 8.4 mm in diameter, dried rapidly and remained substantially intact throughout carbonization and combustion. Devolatilization was complete after about 60 s but extensive freeboard combustion of volatiles was evident. The water content of the coal had very little influence on burnout time. Char combustion dominated the overall combustion process and took place under kinetic control with significant pore burning.     

Combustion kinetics of coke particles in a fluidized bed reactor

Combustion studies with a metallurgical coke have been carried out in batch experiments in an electrically heated fluidized bed reactor. Different experiments were carried out in air at temperatures ranging from 750°C to 950°C and coke particle diameters between 0.675 and 3.500 mm. The reactor outlet concentrations of O₂, CO₂ and CO were monitored continuously. A methodology for estimating the kinetic parameters of char combustion has been developed. From the response of gas outlet concentrations to the batch amount, a parameter to estimate the mean oxygen concentration in the bed was deduced. The overall rate constants at each burnoff stage were also obtained. Particle size of irregular coke particles at different stages of the combustion process were determined by means of image analysis technique. This makes it possible to evaluate the real importance of the external mass transfer resistance during combustion and to estimate the chemical rate constant. The results indicate that the coke particles studied react under Regime II in the size and temperature ranges analysed, though moving to Regime III as long as bed temperature and particle size increase. The estimated mean oxygen concentration around the char particles was in every case lower than that estimated by applying the two-phase theory. The dependence of the chemical rate constant on temperature can be described by the equation k_p[g/(cm² s atm O₂)] = 30 exp(− 22,340/RT_p), where the activation energy is expressed in units of cal/mol.     

Combustion of single char particles in a turbulent fluidized bed

The combustion of single bituminous char particles (4-12 mm diameter) was studied in a turbulent fluidized bed operated at 1098 K using air as the fluidising medium. Results indicated that particles burn with constant density following a shrinking sphere model. Burning rates are much higher than those observed in a bubbling fluidized bed. The rate of transfer of oxygen to the particle surface is also higher than that observed in bubbling beds. A model is proposed to calculate the Sherwood numbers of the burning carbon particles. Experimental values of the Sherwood numbers agree well with those predicted from the model.     

Single char particle combustion at moderate temperature: effects of ash

The effects of ash content, ash layer heat and mass transfer on a single granulated char particle (10–18 mm in diameter) combustion in an air stream (12 cm s⁻¹ in cold base) are studied. The transient temperature of various ash content char particle burning in the surrounding gas temperatures of 900 to 1200 K is simulated. Agreement between simulated and experiment results is obtained by adjusting the ash layer diffusion coefficient and heat conductivity, surface emissivity and the reaction rate constant. The reaction rate constant plays an important role in modeling the initial stage of char particle combustion even when the overall rate is ash layer diffusion controlled. It determines the particle heating rate in the initial stage of combustion, and then indirectly influences the peak temperature. The ash layer diffusion resistance affects the rate controlling processes and the pattern of the time-temperature profile. The higher ash content char particle burns with a lower peak temperature and earlier temperature decrease due to the lower ash layer porosity and lower ash layer diffusion coefficient. It is concluded that the high ash particle combustion is controlled by ash layer diffusion except in the initial stage of combustion. As for the lower ash content char particle, it is controlled mainly by reaction at lower ambient temperature and by film diffusion at a higher temperature in the earlier stage. However, in the last stage, it is controlled by ash layer diffusion. The transition occurs when the ash layer is formed and the diffusion resistance is significant, and it is at that time that the particle reaches its peak temperature.