A simplified model of SO2 capture by limestone in 71 MWe pressurized fluidized bed combustor

A mathematical model of SO₂ capture by uncalcined limestone particles with solid attrition under pressurized fluidized bed combustion conditions was developed based on the shrinking unreacted-core model. Since the thickness of the product layer is sufficiently much smaller than the particle size, a flat surface model was employed. The difference in SO₂ capture behavior between continuous solid attrition and intermittent attrition was investigated. The reaction rate for intermittent solid attrition was found to be lower than that for continuous attrition mode under low SO₂ concentration conditions. A simple mathematical expression to calculate reaction rate of SO₂ capture per unit external surface area of limestone is proposed.The present simplified mathematical model of SO₂ capture by single limestone particle under periodical attrition conditions was applied to the analysis of a large-scale pressurized fluidized bed combustor. By giving the period of attrition as a parameter, the experimental results agreed well with the model results. From the vertical concentration profile of SO₂ concentration, the emission of SO₂ was found to be governed by the balance between SO₂ formation rate from char and SO₂ capture by limestone at the upper surface of the dense bed. A simplified expression to estimate SO₂ emission from pressurized fluidized bed combustors was proposed.     

Comparison among attrition-reaction models of SO2 capture by uncalcined limestone under pressurized fluidized bed combustion conditions

Mathematical models of SO₂ capture by uncalcined limestone (CaCO₃) particles with solid attrition were compared under pressurized fluidized bed combustion conditions. For reaction, we used: (1) a shrinking core model with a distinct border between the product (CaSO₄) layer with a conversion of unity and unreacted core with a conversion of zero, and (2) a distributed reaction model with smooth transition from the unreacted part to the product part with conversion between zero and unity. Continuous attrition and intermittent attrition were compared for attrition. Apparent conversion of the solid was overestimated regardless of the reaction model for continuous attrition. Attrition model plays an important role in determining limestone utilization efficiency, whereas the reaction model played only a minor role.     

Characterization of the reactivity of limestones with SO2 in a fluidized bed reactor

The reaction between SO₂ and calcined limestone particles has been studied in a fluidized bed combustor. Measurements of sorbent reactivity with SO₂ were made for small batches of limestone injected into the combustor. Simultaneous continuous combustion of bituminous coal provided conditions like those of a boiler for study of the sulphation reaction. A semi-empirical rate model of the CaO-SO₂ reaction has been developed. External mass transfer of SO₂, diffusion within the particles and chemical reaction are taken into account. The limestone reactivity with SO₂ is characterized by two parameters which are dependent on the temperature and sorbent particle size. A model for predicting the limestone requirements in a fluidized bed boiler has been developed. Parameters from the batch experiments are included. The predictions for sulfur retention agree with the experimental results. In addition, effects of operating conditions (gas velocity, recycle, limestone particle size) on the retention of SO₂ were simulated using the model.     

Sorbent attrition in a carbonation/calcination pilot plant for capturing CO2 from flue gases

There is increasing interest in CO₂ looping cycles that involve the repeated calcination and carbonation of the sorbent as a way to capture CO₂ from flue gases during the carbonation step and the generation of a pure stream of CO₂ in the oxyfired calcination step. In particular, attrition of the material in these interconnected fluidized bed reactors is a problem of general concern. Attrition of limestone derived materials has been studied in fluidized bed systems by numerous authors. In this work, we have investigated the attrition of two limestones used in a system of two interconnected circulating fluidized bed reactors operating in continuous mode as carbonation and calciner reactors. We observed a rapid initial attrition of both limestones during the calcination step which was then followed by a highly stable period (up to 140 h of added circulation for one of the limestones) during which particle size changes were negligible. This is consistent with previous observations of attrition in other systems that employ these materials. However, a comparison of the attrition model constants with the data reported in the literature showed the two limestones to be particularly fragile during the initial calcination and the first few hours of circulation. Thus, a careful choice of limestone based on its attrition properties must be taken into account in designing future carbonate looping systems.     

Sulfur dioxide release in fluidized bed combustion of Jorban oil shale

Due to high concentrations of sulfur and carbonates in Jordan oil shale, it was anticipated that the deposits would be a suitable burning fuel in an atmospheric fluidized bed system. The SO₂, capture by calcium oxide and calcined dolomite in spent shale prompted this experimental program to verify spent shale reactivity and SO₂ retention. Concentrations of SO₂, in effluents were analyzed vs. time in a fluidized bed material of silica sand, pure limestone rock (99.6% carbonates) and spent shale. The SO₂, release was studied in batch tests for each bed material. The effect of particle size in spent shale FBC was tested.Some model sulfur containing compounds were impregnated on limestone carrier solids and combusted to give time-release data. A sample of pyrite was charged to the bed of limestone sand in order to study its sulfur release and compare the data. A component balance was attempted to trace sulfur in the various bed materials.     

The combined effect of H2O and SO2 on the simultaneous calcination/sulfation reaction in CFBs

The combined effect of H₂O and SO₂ on the reaction kinetics and pore structure of limestone during simultaneous calcination/sulfation reactions under circulating fluidized bed (CFB) conditions was first studied in a constant-temperature reactor. H₂O can accelerate the sulfation reaction rate in the slow-sulfation stage significantly but has a smaller effect in the fast-sulfation stage. H₂O can also accelerate the calcination of CaCO₃, and should be considered as a catalyst, as the activation energy for the calcination reaction was lower in the presence of H₂O. When the limestone particles are calcining, SO₂ in the flue gas can react with CaO on the outer particle layer and the resulting CaSO₄ blocks the CaO pores, increases the diffusion resistance of CO₂, and, in consequence, decreases the calcination rate of CaCO₃. Here, gases containing 15% H₂O and 0.3% SO₂ are shown to increase the calcination rate. This means that the accelerating effect of 15% H₂O on CaCO₃ decomposition is stronger than the impeding effect caused by 0.3% SO₂. The calcination rate of limestone particles was controlled by both the intrinsic reaction and the CO₂ diffusion rate in the pores, but the intrinsic reaction rate played a major role as indicated by the effectiveness factors determined in this work. This may explain the synergic effect of H₂O and SO₂ on CaCO₃ decomposition observed here. Finally, the effect of H₂O and SO₂ on sulfur capture in a 600 MWe CFB boiler burning petroleum coke is also analyzed. The sulfation performance of limestone evaluated by simultaneous calcination/sulfation is shown to be much higher than that by sulfation of CaO. Based on our calculations, a novel use of the wet flue gas recycle method was put forward to improve the sulfur capture performance for high-sulfur low-moisture fuels such as petroleum coke. © 2019 American Institute of Chemical Engineers AIChE J, 65: 1256–1268, 2019     

CO2 capture from flue gases using a fluidized bed reactor with limestone

The CO₂ capture from flue gases by a small fluidized bed reactor was experimentally investigated with limestone. The results showed that CO₂ in flue gases could be captured by limestone with high efficiency, but the CO₂ capture capacity of limestone decayed with the increasing of carbonation/calcination cycles. From a practical point of view, coal may be required to provide the heat for CaCO₃ calcination, resulting in some potential effect on the sorbent capacity of CO₂ capture. Experiment results indicated that the variation in the capacity of CO₂ capture by using a limestone/coal ash mixture with a cyclic number was qualitatively similar to the variation of the capacity of CO₂ capture using limestone only. Cyclic stability of limestone only undergoing the kinetically controlled stage in the carbonation process had negligible difference with that of the limestone undergoing both the kinetically controlled stage and the product layer diffusion controlled stage. Based on the experimental data, a model for the high-velocity fluidized bed carbonator that consists of a dense bed zone and a riser zone was developed. The model predicted that high CO₂ capture efficiencies (>80%) were achievable for a range of reasonable operating conditions by the high-velocity fluidized bed carbonator in a continuous carbonation and calcination system.     

High temperature desulphurization by fine limestone during staged fluidized‐bed combustion

This paper reviews the SO₂ emission from a 0.3 m² stainless‐steel fluidized‐bed combustor. Fine coal was premixed with fine limestone and fed pneumatically under the bed. The SO₂ emission was found to depend largely on air staging ratio and bed temperature, which agrees with previous observations. The SO₂ emission observed in sorbent‐free tests (reported earlier by Khan and Cibbs, 1995) was found to be proportional to the sulphur content of the fuel when limestone was added, the sulphur capture at a fixed Ca/S molar ratio was dependent on oxygen stoichiometry and bed temperature. Finely sized limestone enhanced the effectivity of the sorbent at low bed temperature and air staging ratio. During staged combustion, the combustion efficiency depended largely on primary air to coal ratio. Around 90% combustion efficiency was observed at 1 m/s fluidizing velocity which was reduced when fluidizing velocity was increased to 1.5 and 2 m/s. This reduction is due to increased elutriation of finer coal particles from the combustor.     

An experimental study on the primary fragmentation and attrition of limestones in a fluidized bed

In this paper, an experimental study on the primary fragmentation and attrition of 5 limestones in a fluidized bed was conducted. The intensity of fragmentation and attrition were measured in the same apparatus but at different fluidizing velocities. It was found that the averaged size of the particles decreased by about 10-20% during the fragmentation process. The important factors for particle comminution include limestone types, heating rate, calcination condition and ambient CO₂ concentration. Fragmentation mainly occurred in the first a few minutes in the fluidized bed and it was more intense than that in the muffle furnace at the same temperature. The original size effect was ambiguous, depending on the limestone type. The comminution caused by attrition mainly occurred during calcination process rather than sulphation process. The sulphation process was fragmentation and attrition resisted. The attrition rate of sulphate was similar to that of lime in trend, decaying exponentially with time, but was one-magnitude-order smaller than that of lime. Present experimental results indicate that fragmentation mechanism of the limestone is dominated by CO₂ release instead of thermal stress.     

Effects of fuel type and operating conditions on SO2 emission in fluidized bed combustion

The SO₂ emission from six fluidized bed combustors was examined. Approximately 71.5% of the fuel sulphur was found to be emitted as SO₂ in sorbent-free tests. General observations on the effects of Ca/S molar ratio, limestone size and recycle systems are presented. The effects of limestone type and superficial velocity were found to be insignificant, as was the effect of bed temperature in the range 800-950°C. In tests with fine solid and liquid fuels, circulating FBC's were found to provide significantly better sulphur capture than bubbling FBC's.     

Effects of operational parameters on emission performance and combustion efficiency in small-scale CFBCs

A well-designed CFBC can burn coal with high efficiency and within acceptable levels of gaseous emissions. In this theoretical study effects of operational parameters on combustion efficiency and the pollutants emitted have been estimated using a developed dynamic 2D (two-dimensional) model for CFBCs. Model simulations have been carried out to examine the effect of different operational parameters such as excess air and gas inlet pressure and coal particle size on bed temperature, the overall CO, NO_x and SO₂ emissions and combustion efficiency from a small-scale CFBC. It has been observed that increasing excess air ratio causes fluidized bed temperature decrease and CO emission increase. Coal particle size has more significant effect on CO emissions than the gas inlet pressure at the entrance to fluidized bed. Increasing excess air ratio leads to decreasing SO₂ and NO_x emissions. The gas inlet pressure at the entrance to fluidized bed has a more significant effect on NO_x emission than the coal particle size. Increasing excess air causes decreasing combustion efficiency. The gas inlet pressure has more pronounced effect on combustion efficiency than the coal particle size, particularly at higher excess air ratios. The developed model is also validated in terms of combustion efficiency with experimental literature data obtained from 300 kW laboratory scale test unit. The present theoretical study also confirms that CFB combustion allows clean and efficient combustion of coal.     

Flue gas desulfurization under simulated oxyfiring fluidized bed combustion conditions: The influence of limestone attrition and fragmentation

Flue gas desulfurization by means of limestone injection under simulated fluidized bed oxyfiring conditions was investigated, with a particular focus on particle attrition and fragmentation phenomena. An experimental protocol was applied, based on the use of complementary techniques that had been previously developed for the characterization of attrition of sorbents in air-blown atmospheric fluidized bed combustors. The extent and pattern of limestone attrition by surface wear in the dense phase of a fluidized bed were assessed in bench scale fluidized bed experiments under simulated oxyfiring conditions. Sorbent samples generated during the oxyfiring tests were further characterized from the standpoint of fragmentation upon high velocity impact by means of a particle impactor. The experimental results were compared with those previously obtained with the same limestone under air-blown atmospheric fluidized bed combustion conditions. The profound differences in the attrition and fragmentation extents and patterns associated with oxyfiring as compared to air-blown atmospheric combustion and the role played by the different attrition/fragmentation paths were highlighted. In particular, it was noted that attrition could effectively enhance particle sulfation under oxyfiring conditions by continuously disclosing unconverted calcium to the sulfur-bearing atmosphere.     

Modelling of CO2, CO, SO2, O2 and NOx emissions from the oxy-fuel combustion in a circulating fluidized bed

The paper presents a model of coal combustion in air and oxygen-enriched CFB environment. A computer program to calculate the CO₂, CO, SO₂, NO_x and O₂ emissions from the combustion of solid fuels in a circulating fluidized bed boiler was created. The validity of this program was verified by measurements on a 0.1MW_th OxyFuel-CFB Test Rig.The calculations have been carried out for air and so-called oxy-fuel conditions, i.e. when combustion runs in a gas mixture based on O₂ and N₂, with various fractions of oxygen.The comparison between measured and predicted by model CO, SO₂, NO_x and O₂ emissions is shown in this paper. The results of the calculation showed, that the kinetic equations of some reaction have to be modified. Authors propose to use the reaction surface area instead of the specific internal surface area of char in rate constant formulas as the combustion nature changes from internal-kinetic to external-diffusion controlling regime.     

A method of evaluating limestone reactivity with SO2 under fluidized bed combustion conditions

The reactivity of limestone with sulphur dioxide has been evaluated during conditions similar to those existing in a fluidized bed combustor using a fixed-bed quartz reactor. The reactivity of up to 11 particle sizes of 2 limestones were evaluated, and an exponential decay function was found to best describe the rate behaviour versus conversion of CaO to CaSO₄. The two constants in the exponential decay approximation could both be expressed as functions of particle size. Subsequently, the limestone reactivity as a function of both size and conversion could be reasonably well described by a total of 4 to 6 constants. An analytical sulphur capture model for fluidized bed boilers (FBB) that incorporates this type of reactivity function is proposed.     

Effects of steam on the sulfation of limestone and NOx formation in an air- and oxy-fired pilot-scale circulating fluidized bed combustor

The existing fluidized bed combustion literature on sulfation shows that above 30% conversion, direct sulfation via reaction with CaCO₃ is faster than indirect sulfation with CaO. However, while this is true for dry flue gases, it is not the case if steam (H₂O_(g)) is present at realistic levels for coal combustion, and it has been confirmed by experiments employing thermogravimetric analysis (TGA) and tube furnace (TF) testing that direct sulfation is in fact slower than indirect sulfation for nearly all levels of conversion if steam (H₂O_(g)) is present. In this work we have also examined the effects of H₂O_(g) on SO₂ capture and NH₃ oxidation to NO_x over calcium-containing compounds under air- and oxy-fired conditions in a pilot-scale circulating fluidized bed combustor (CFBC) utilizing limestone addition. The results of the pilot-scale tests confirm suggestions from our previous work that sulfur capture from the air firing of low-moisture fuels benefits from steam-sulfation. For petroleum coke, the addition of 8%vol H₂O_(g) resulted in increased SO₂ retention and Ca utilization, as well as decreased NO_x emissions by up to 44%. The simultaneous reduction of SO₂ and NO_x was attributed to enhanced solid-state diffusion (sintering) by H₂O_(g). Under oxy-fuel-firing conditions, H₂O_(g) addition also resulted in decreased NO_x emissions, but the pilot-scale tests showed poorer sulfur capture performance and calcium utilization as compared to air firing when H₂O_(g) was present, thereby reconfirming the TGA/TF results. It appears that most bench-scale work on sulfation to date has underestimated the true rate of reaction for sulfation in the presence of H₂O_(g). This conclusion explains at least in part why indirect sulfation is often faster than direct sulfation in pilot plant studies on oxy-fuel circulating fluidized bed combustion. Moreover, this work stresses the importance of including H₂O_(g) in bench-scale experiments that attempt to simulate real combustion environments.     

Enhancement of direct sulfation of limestone by Na2CO3 addition

For an oxy-fuel circulating fluidized bed combustion system, the limestone calcination is normally prevented due to excessive CO₂ partial pressures and the limestone is subject to a direct sulfation reaction. The enhancement of the direct sulfation of limestone by Na₂CO₃ was investigated under high CO₂ partial pressure in a thermogravimetric apparatus (TGA) and scanning electron microscope (SEM) analysis method. A commercial limestone with a mean size of 18.8 μm was used. Experimental results indicate that the incorporation of Na⁺ ions in solid product CaSO₄ lattice structures results in formation of more extrinsic point defects in the crystal lattices of CaSO₄ and a significantly increased solid-state diffusivity/mobility in the solid product. So the direct sulfation of Na₂CO₃-doped limestone shows higher rate and higher degree of conversion in the later stage of sulfation, in comparison with the direct sulfation of original limestone. The reaction changes from diffusional control to chemical reaction control in the presence of Na₂CO₃ because of the effect of foreign ions on accelerating the solid-state diffusion.     

氧燃烧方式下石灰石直接固硫反应模拟

氧燃烧方式下高浓度CO2气氛使得石灰石与SO2的气固反应存在直接固硫和间接固硫两种方式。在热重分析仪上进行了石灰石直接硫化的实验,考察了温度、SO2浓度对直接固硫反应的影响。基于球形颗粒气体扩散理论,在未反应收缩核模型的基础上推导出一种从实验数据计算化学反应速率常数和SO2反应级数的新方法。同时在已有研究的基础上改进了产物层扩散系数的计算方法,并采用未反应收缩核模型对不同温度、SO2浓度条件下石灰石直接固硫反应进行模拟,模拟结果与实验结果较为吻合。在所建立模型的基础上定性讨论了温度、孔隙率、平均孔径对产物层有效扩散系数的影响,发现温度对有效扩散系数影响很显著,而孔隙率、平均孔径的影响较小。     

Methods for measuring the concentrations of SO2, and of gaseous reduced sulphur compounds in the combustion chamber of a circulating fluidized bed boiler

The present work was aimed at developing and improving methods for measurement of gaseous sulphur compounds in the combustion chamber of a fluidized bed boiler (FBB). The sampling of SO₂ was improved by removing NH₃ and H₂O with a sorbent immediately after the probe. The concentration of reduced sulphur species was determined by means of two conventional SO₂ analyzers and an intermediate converter, where the reduced species are oxidized to SO₂. Gas phase sulphides were also sampled with a gas quenching probe by means of a basic solution which was subsequently analysed by wet chemistry. The methods were tested during coal combustion in a 12 MW circulating FBB without limestone for two cases of air‐staging.     

Calcium-based sorbents behaviour during sulphation at oxy-fuel fluidised bed combustion conditions

Sulphur capture by calcium-based sorbents is a process highly dependent on the temperature and CO₂ concentration. In oxy-fuel combustion in fluidised beds (FB), CO₂ concentration in the flue gas may be enriched up to 95%. Under so high CO₂ concentration, different from that in conventional coal combustion with air, the calcination and sulphation behaviour of the sorbent must be defined to determine the optimum operating temperature in the FB combustors.In this work, the SO₂ retention capacity of two different limestones was tested by thermogravimetric analysis at typical oxy-fuel conditions in FB combustors. The effect of the main operating variables affecting calcination and sulphation reactions, like CO₂ and SO₂ concentrations, temperature, and sorbent particle size, was analysed.It was observed a clear difference in the sulphation conversion reached by the sorbent whether the sulphation takes place under indirect or direct sulphation, being much higher under indirect sulphation. But, in spite of this difference, for a given condition and temperature, the CO₂ concentration did not affect to the sulphation conversion, being its major effect to delay the CaCO₃ decomposition to a higher temperature.For the typical operating conditions and sorbent particle sizes used in oxy-fuel FB combustors, the maximum sorbent sulphation conversions were reached at temperatures of about 900 °C. At these conditions, limestone sulphation took place in two steps. The first one was controlled by diffusion through porous system of the particles until pore plugging, and the second controlled by the diffusion through product layer. As a consequence, the maximum sulphation conversion increased with decreasing the particle size and increasing the SO₂ concentration.