Development of an apparatus for on-line analysis of unburned carbon in fly ash using laser-induced breakdown spectroscopy (LIBS)

The level of unburned carbon in fly ash is an important criteria for evaluating the combustion efficiencies of boilers, as well as the commercial value of the produced fly ash. In this work, an automated prototype laser-induced breakdown spectroscopy (LIBS) apparatus comprising an isokinetic sampler, a sample preparation module, and a LIBS module has been developed for possible application to power plants for on-line analysis of unburned carbon in fly ash without being affected by the type of coal burned. Emphasis is placed on the structure and operation of the LIBS apparatus, the optimum suction capacity selection, the analytical methods for estimation of the exact C line intensity, and the proper calibration model established for minimizing the matrix effects, which enable the minimization of matrix effects and obtaining more accurate compositional measurements. Good agreement has been found between the laboratory measurement results from the LIBS method and those from the traditional method. The measurement accuracy presented here for unburned carbon analysis is estimated to be 0.26%, while the average relative error is 3.81%.     

Unburned carbon measurement in fly ash using laser-induced breakdown spectroscopy with short nanosecond pulse width laser

The unburned carbon in fly ash is one of the important factors for the boiler combustion condition. Controlling the unburned carbon in fly ash is beneficial for fly ash recycle and to improve the combustion efficiency of the coal. Laser-induced breakdown spectroscopy (LIBS) technology has been applied to measure the fly ash contents due to its merits of non-contact, fast response, high sensitivity, and real-time measurement. In this study, experimental measurements have been adopted for fly ash flows with the surrounding gases of N₂ and CO₂, while the CO₂ concentration varified to evaluate the CO₂ effect on the unburned carbon signal from fly ash powder. Two kinds of pulse width lasers, 6?ns and 1?ns, were separately adopted to compare the influence of laser pulse width. Results showed that compared with that using 6?ns pulse width laser, plasma temperature was lower and had less dependence on delay time when using 1?ns pulse width laser, and spectra had more stable background. By using 1?ns pulse width laser, the emission signal from surrounding CO₂ also decreased because of the less surrounding gas breakdown. The solid powder breakdown signals also became more stable when using 1?ns pulse width laser. It is demonstrated that 1?ns pulse width laser has the merits for fly ash flow measurement using LIBS.     

Quantitative analysis of carbon content in fly ash using LIBS based on support vector regression

Laser-induced breakdown spectroscopy (LIBS) has been proved as an on-line detection technology to measure the carbon content in fly ash, which is beneficial for immediate assessment of the boiler combustion efficiency. Support vector regression (SVR) was adopted as the quantitative model for the carbon content measurement in fly ash in this study. Ash species was one of the key factors affecting quantitative accuracy. Experiments have proven that, the index of plasma temperature and the electron density among different species could be similar, while the partition function ratios and the temperature correction factor showed obvious differences among different ash species. Based on the partition function ratios, the Matrix Effect Correction Factor (MECF) was defined. SVR model was optimized by MECF and the analysis results showed that the correlation coefficient of calibration (R²) increased from 0.989 to 0.991, the root-mean-square error of calibration (RMSEC) decreased from 2.02% to 0.850%, the root-mean-square error of prediction (RMSEP) decreased from 2.13% to 1.07%, and averaged relative standard deviation (ARSD) decreased from 8.62% to 1.89%. The results showed that SVR combined with MECF was an effective method to improve the accuracy of LIBS quantitative analysis of the carbon content in fly ash.     

基于蚁群神经网络的飞灰含碳量测量方法

飞灰含碳量是衡量电站锅炉燃烧效率的重要参数。飞灰含碳量的准确测量有助于调整锅炉燃烧,提高锅炉运行的经济性和安全性。本文采用了蚁群神经网络算法,利用蚁群算法对神经网络进行优化,将优化过后的神经网络用于飞灰含碳量的预测,并分析了经过蚁群神经算法与遗传神经网络的预测效果。     

Model of the diffuse reflectivity of fly ash and its application to an optical sensor system for the determination of carbon in fly ash

Fly ash, a fine gray powder, is filtered out of the flue gas in coal-fired power stations. It consists of silicon oxide, metal oxides, and unburned carbon. An optical sensor system for measurement of the carbon content of fly ash is described. Based on a mathematical model, an algorithm is deduced that allows the carbon content to be calculated from two measurements of the diffuse reflectivity of a fly ash sample before and after a surface-grinding process. In this model the fly ash sample is assumed to be composed of three types of cube: light-scattering cubes, soft absorbing cubes (carbon), and hard absorbing cubes (iron oxide).     

The role of weathering on fly ash charge distribution during triboelectrostatic beneficiation

Triboelectrostatic beneficiation of coal combustion fly ashes with high-unburned carbon contents can produce low-carbon ash products having value as mineral admixtures and meeting technical requirements for replacing cement in concrete. This capability is a result of establishing bipolar charge on mineral ash versus carbon particles where, typically, unburned carbon attains positive surface charge and ash attains negative surface charge under the tribocharging conditions employed in triboelectrostatic technologies. However, long-term exposure of fly ash to weathering conditions, such as moisture or high humidity, before beneficiation is known to dramatically diminish carbon-ash separation efficiencies. Although experimentation has shown that water soluble surface species can be redistributed on fly ash particles after exposure to moisture, which could affect the extent of charging and polarities, measurement of the actual amount of charge and polarity on particles after weathering exposure versus after removal of surface moisture has not been accomplished. Hence, a new experimental methodology was developed and applied to measure charge distributions on tribocharged ash and carbon particles in a fly ash that had been exposed to weathering conditions for 6 months before and after removal of the surface moisture. Weathered ash particles were found to have an average zero charge, whereas carbon particles attained an average negative charge, opposite of the normal polarity for carbon. Although the extent of uncharged particles decreased and ash particles attained an average negative charge after drying, carbon particles attained only an average zero charge. These changes were reflected in very small increases in carbon-ash separation efficiency, in contrast to previous beneficiation tests in which fly ash drying led to significant increases in carbon-ash separation efficiency. It is suggested that removal of surface moisture in the absence of other processes like surface ion redistribution would beneficially impact carbon-ash triboelectrostatic beneficiation.     

Environmental-benign utilisation of fly ash as low-cost adsorbents

Fly ash is a waste substance from thermal power plants, steel mills, etc. that is found in abundance in the world. In recent years, utilisation of fly ash has gained much attention in public and industry, which will help reduce the environmental burden and enhance economic benefit. In this paper, the technical feasibility of utilisation of fly ash as a low-cost adsorbent for various adsorption processes for removal of pollutants in air and water systems has been reviewed. Instead of using commercial activated carbon or zeolites, a lot of researches have been conducted using fly ash for adsorption of NO(x), SO(x), organic compounds, and mercury in air, and cations, anions, dyes and other organic matters in waters. It is recognised that fly ash is a promising adsorbent for removal of various pollutants. Chemical treatment of fly ash will make conversion of fly ash into a more efficient adsorbent for gas and water cleaning. Investigations also revealed that unburned carbon component in fly ash plays an important role in adsorption capacity. Directions for future research are also discussed.     

Investigations on the influence of fly ash on the formation and stability of artificially entrained air voids in concrete

In concrete, fly ash is applied to a task-oriented improvement of different properties. Besides the advantages, e.g. the improvement of the rheology of the fresh concrete or the density of the hardened concrete, some investigations and the experience from practice indicate that some fly ashes probably influence the formation and stability of artificially entrained air voids. The reason lies presumably in the fraction of unburned carbon, a minor component of the fly ash. To identify the causes, seven fly ashes from European power plants were investigated. The fly ashes were characterized and mortar and concrete tests were conducted to identify specific fly ash parameters which might be responsible for the impaired formation and stability of the air voids. Furthermore, it was examined whether the foam index test is applicable for the assessment of the air entraining agent demand and whether an adequate accuracy of the results is given. On the basis of the results it was also examined whether the mortar tests or a fly ash specific parameter can be applied as an alternative prediction tool to assess the air entraining agent demand for an air entrained concrete.     

气力输送在锅炉飞灰回燃技术中的应用

以山东省内几家热电厂75、130t/h循环流化床锅炉飞灰回燃、热效率提高为例,介绍气力输送系统在热电厂飞灰回燃过程中的应用,对热电厂飞灰含碳量高的原因进行分析,详细分析飞灰回燃系统的工艺流程,并对飞灰回燃前后的含碳量及成本进行对比。结果显示:飞灰回燃技术能够显著提高煤炭的燃烧率,提高锅炉的热效率。     

Extracting coal ash content from laser-induced breakdown spectroscopy (LIBS) spectra by multivariate analysis

Laser-induced breakdown spectroscopy (LIBS) combined with partial least squares (PLS) analysis has been applied for the quantitative analysis of the ash content of coal in this paper. The multivariate analysis method was employed to extract coal ash content information from LIBS spectra rather than from the concentrations of the main ash-forming elements. In order to construct a rigorous partial least squares regression model and reduce the calculation time, different spectral range data were used to construct partial least squares regression models, and then the performances of these models were compared in terms of the correlation coefficients of calibration and validation and the root mean square errors of calibration and cross-validation. Afterwards, the prediction accuracy, reproducibility, and the limit of detection of the partial least squares regression model were validated with independent laser-induced breakdown spectroscopy measurements of four unknown samples. The results show that a good agreement is observed between the ash content provided by thermo-gravimetric analyzer and the LIBS measurements coupled to the PLS regression model for the unknown samples. The feasibility of extracting coal ash content from LIBS spectra is approved. It is also confirmed that this technique has good potential for quantitative analysis of the ash content of coal.     

330 MW循环流化床锅炉燃烧调整试验研究

为解决某330 MW循环流化床（circulating fluidized bed,CFB）锅炉运行床温分布不均匀、炉内受热面磨损爆管等问题,进行了锅炉的燃烧优化调整试验。结果表明,通过优化一次风量、总风量及风室压力等关键运行参数,确定了最佳运行工况及参数,降低了锅炉灰渣平均可燃物含量,使锅炉热效率提高0.85%。燃烧优化调整试验还使一、二次风机总功率降低了0.8 MW,厂用电率相应降低了0.24%,锅炉的运行安全性和经济性由此得到进一步提高。     

Polychlorinated biphenyls removal from weathered municipal solid waste incineration fly ash by collector-assisted column flotation

Polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are highly toxic micropollutants emitted from municipal solid waste incineration (MSWI), in particular, concentrated in the unburned carbon (UC) of MSWI fly ash. Because of concerns over their adverse health effects, a number of countries have classified MSWI fly ash as hazardous material and required further treatment before its final disposal in landfills. The technologies for removing the toxic chlorinated micropollutants in the MSWI fly ash have been studied, however, until now no mature technique has been obtained in this purpose. In this research, we used a technique of collector-assisted column flotation to remove PCBs-enriched UC from MSWI fly ash. We found that 36.9% PCBs could be removed from fresh MSWI fly ash with 61.7% UC removal efficiency, whereas only 21.7% PCBs could be removed from weathered MSWI fly ash with a low UC removal efficiency of 33.7%. By adding a mixture of two kinds of surfactants: sorbitan mono-oleate and polyoxyethylene (20) sorbitan mono-oleate to the weathered fly ash slurry as the collector assistant, 39.3% PCBs was removed at the hydrophile–lipophile balance (HLB) value of 13.5, while the UC removal efficiency increased to 49.0%. The results showed that the collector assistant could enhance PCBs and UC removal efficiencies during the column flotation process, and the mechanism has been discussed in detail. Higher PCBs and UC removal efficiencies could be expected by further optimizing the conditions of collector-assisted column flotation.     

Dye adsorption on unburned carbon: kinetics and equilibrium

Unburned carbon in fly ash is an important by-product from coal combustion. In this investigation, unburned carbon has been separated from fly ash and been employed as a low cost adsorbent for a basic dye adsorption (Rhodamine B) in aqueous solution. Adsorption isotherm and kinetics of adsorption have been investigated using batch experiments. It is found that dye adsorption capacity depends on initial concentration, pH of solution, and temperature. The adsorption isotherm can be described by Langmuir model and the adsorption capacity of Rhodamine B at 30, 40, and 50 degrees C can reach 9.7 x 10(-5), 1.14 x 10(-4), and 1.5 x 10(-4)mol g(-1), respectively. The pseudo first- and second-order kinetic models have been employed to fit the dynamic adsorption. It is found that the dynamic adsorption follows the pseudo second-order model. Thermodynamic calculations indicate that the adsorption is endothermic reaction with DeltaH degrees at 25 kJ mol(-1).     

Explosibility boundaries for fly ash/pulverized fuel mixtures

Incomplete combustion and subsequent fuel contamination of a waste stream can pose a serious explosion hazard. An example of this type of incident is the contamination of fly ash with unburned pulverized coal. The coal, if present in sufficient quantities in the mixture, can act as a fuel source for a potential explosion. Experiments were conducted in a 20l Siwek explosibility test chamber to determine the minimum fuel contamination of fly ash required to form an explosible mixture. A sample of fly ash from Ontario Power Generation (OPG) (Ont., Canada) was artificially contaminated with Pittsburgh pulverized coal dust (the surrogate used to represent unburned fuel dust). Additionally, the influence of fly ash particle size on the amount of fuel contaminant required to form an explosible mixture was examined. Fine and coarse size fractions of fly ash were obtained by screening the original sample of OPG fly ash.The results show that at least 21% Pittsburgh pulverized coal (or 10% volatile matter) was required to form an explosible mixture of the original fly ash sample and coal dust. The results also illustrate that fly ash particle size is important when examining the explosibility of the mixture. The fine size fraction of fly ash required a minimum of 25% coal dust (12% volatile matter) in the mixture for explosibility, whereas the coarse fly ash required only 10% coal dust (7% volatile matter). Thus, the larger the particle size of the inert fly ash component in the mixture, the greater the hazard.     

电厂锅炉优化改造试验分析

为进一步提高锅炉效率,减少锅炉污染物排放,以某电厂锅炉为研究对象,对锅炉的空预器密封装置、水平烟道吹灰系统以及高压省煤器进行等进行整体优化,对锅炉进行化学清洗和保温处理,通过试验对优化前后对锅炉热效率及污染物排放进行对比。结果表明：与改造前相比,不同负荷下锅炉效率平均提高2.3%,同时供电煤耗降低;锅炉排烟温度降低,干烟气热损失减少;未燃尽率碳热损失及空预器漏风率也大幅降低,锅炉排放NOx浓度达到排放要求。此次优化改造达到了预期效果。     

Interactions between mercury and dry FGD ash in simulated post combustion conditions

Two different flue gas desulfurization (FGD) ash samples were exposed to a simulated flue gas stream containing elemental mercury vapor to evaluate the interactions and determine the effects of gas components, dry FGD ash samples, and temperature on adsorption and heterogeneous oxidation of mercury. Both samples were characterized for surface area, unburned carbon content, element content, and mineralogical composition. Mercury speciation downstream from the sample was determined using Ontario Hydro Method. Results showed that higher levels of mercury oxidation were associated with higher levels of mercury capture. The NO(2), HCl, and Cl(2) promoted mercury oxidation, while SO(2) and NO had inhibitory effects on mercury oxidation. Unburned carbon of dry FGD ash sample played an important role in mercury capture. Whether the surface area was caused by unburned carbon or by calcium-based sorbents might be more significant than the level of surface area. Extent of mercury oxidation and capture increased slightly and then decreased as the temperature rising due to the interaction of mass transfer and reaction rates control.     

Comparative study of adsorption properties of Turkish fly ashes. II. The case of chromium (VI) and cadmium (II)

The purpose of the study described in this paper was to compare the removal of Cr(VI) and Cd(II) from an aqueous solution using two different Turkish fly ashes; Afsin-Elbistan and Seyitomer as adsorbents. The influence of four parameters (contact time, solution pH, initial metal concentration in solution and ash quality) on the removal at 20+/-2 degrees C was studied. Fly ashes were found to have a higher adsorption capacity for the adsorption of Cd(II) as compared to Cr(VI) and both Cr(VI) and Cd(II) required an equilibrium time of 2h. The adsorption of Cr(VI) was higher at pH 4.0 for Afsin-Elbistan fly ash (25.46%) and pH 3.0 for Seyitomer fly ash (30.91%) while Cd(II) was adsorbed to a greater extent (98.43% for Afsin-Elbistan fly ash and 65.24% for Seyitomer fly ash) at pH 7.0. The adsorption of Cd(II) increased with an increase in the concentrations of these metals in solution while Cr(VI) adsorption decreased by both fly ashes. The lime (crystalline CaO) content in fly ash seemed to be a significant factor in influencing Cr(VI) and Cd(II) ions removal. The linear forms of the Langmuir and Freundlich equations were utilised for experiments with metal concentrations of 55+/-2mg/l for Cr(VI) and 6+/-0.2mg/l for Cd(II) as functions of solution pH (3.0-8.0). The adsorption of Cr(VI) on both fly ashes was not described by both the Langmuir and Freundlich isotherms while Cd(II) adsorption on both fly ashes satisfied only the Langmuir isotherm model. The adsorption capacities of both fly ashes were nearly three times less than that of activated carbon for the removal of Cr(VI) while Afsin-Elbistan fly ash with high-calcium content was as effective as activated carbon for the removal of Cd(II). Therefore, there are possibilities for use the adsorption of Cd(II) ions onto fly ash with high-calcium content in practical applications in Turkey.     

Analytical model for erosion behaviour of impacted fly-ash particles on coal-fired boiler components

Fly ash particles entrained in the flue gas from boiler furnaces in coal-fired power stations can cause serious erosive wear on steel surfaces along the flow path. Such erosion can significantly reduce the operational life of the boiler components. A mathematical model embodying the mechanisms of erosion on behaviour, has been developed to predict erosion rates of coal-fired boiler components at different temperatures. Various grades of steels used in fabrication of boiler components and published data pertaining to boiler fly ash have been used for the modelling. The model incorporates high temperature tensile properties of the target metal surface at room and elevated temperatures and has been implemented in an user-interactive in-house computer code (EROSIM-1), to predict the erosion rates of various grades of steel. Predictions have been found to be in good agreement with the published data. The model is calibrated with plant and experimental data generated from a high temperature air-jet erosion-testing facility. It is hoped that the calibrated model will be useful for erosion analysis of boiler components.     

燃煤电站利用飞灰脱汞的研究现状

汞的累积性及高毒性使其成为了未来主要的污染物控制对象之一,目前较为成熟的活性炭喷射技术平均汞脱除率能够达到80%-98%,但极高的运行成本仍然难于达到大范围商业推广的要求。飞灰作为燃煤电站的废弃物,成本极低,且同样具备汞捕集能力,某些飞灰的汞脱除能力甚至能够达到商业活性炭级别。本文对目前影响飞灰汞脱除率的研究进行了综述。综合讨论了烟气气氛、煤炭类型、飞灰含碳量、飞灰岩相结构等多种因素对飞灰汞脱除率的影响。明确了飞灰脱汞技术的可行性,以及未来亟待解决的问题。     

粉煤灰提取白炭黑和氧化铝的研究

粉煤灰是我国当前排量最大的工业废渣之一,年排渣量已达3亿t以上,大量堆积的粉煤灰会对自然生态环境造成严重的危害。综合利用粉煤灰,实现粉煤灰的资源化利用,对于治理粉煤灰的污染具有十分重要的意义。文章提出先采用碱液常压浸出粉煤灰,生产白炭黑,然后采用碱石灰烧结法生产氧化铝,可实现粉煤灰的经济综合利用。研究表明：用苛性碱液在常压（＜125 ℃）下浸取粉煤灰45 min,粉煤灰中硅的提取率达到72.5 %以上,而氧化铝的总溶出率＜1.2 %;碳分浸取得到的硅酸钠溶液,可以生产氧化硅含量＞99 %的优质白炭黑,溶液中氧化硅转化率＞98 %;浸取硅后的渣中氧化铝含量＞55 %,氧化硅含量＜20 %,铝硅比≥2.7,适宜采用碱石灰烧结法生产氧化铝。碱石灰烧结法适宜的配方为：碱比 0.95～1.0,钙比 1.8～2.0;烧结温度宜为1 200～1 250 ℃;熟料溶出温度75～85 ℃,时间10～20 min,氧化铝回收率＞86 %。综合利用粉煤灰生产白炭黑和氧化铝,经济效益和社会效益显著。