不同来源煤灰激光诱导击穿光谱测量特性对比研究

飞灰含碳量的定量分析需要不同含碳量梯度的飞灰样品作为定标之用。通常做法是用煤粉按照快速灰化法的要求灼烧得到不同含碳量的灰样,用于定标分析。但是这与实际锅炉飞灰的成分存在一定差异,需要对光谱特性的差异进行研究来指导实际定标工作。因此,对比了快速灰化法制备的不同含碳量的煤灰样品与锅炉飞灰在特征谱线强度、等离子温度等等离子光谱特征方面的差异。实验证明快速灰化法制备的煤灰样品的Fe,Mg和Al谱线强度强于锅炉飞灰样品,飞灰等离子温度低于所制备的煤灰样品的等离子体温度,这可能是不同处理过程的物理化学特性差异造成的。用主成分分析法考察了导致光谱差异的主要原因,认为Fe,Mg,Al和Si等元素是导致二者在光谱特性差异的主要因素,这可能因为实验室内按照快速灰化法进行制样的飞灰相应矿物质组成不同所导致的。在用灼烧后的煤灰定标未燃碳时,应注意由于成灰过程不同所造成的Fe,Mg,Al和Si等元素含量和形态不同所带来的影响。     

减少二氧化碳对LIBS检测飞灰中未燃碳含量影响的研究

通常热力发电厂将飞灰中未燃碳的含量作为评价锅炉燃烧效率的重要指标,通过测量飞灰中未燃碳的含量来评价煤粉燃烧的充分程度,进而实现优化燃烧、提高机组效率。基于激光诱导击穿光谱技术(LIBS)无接触、快速响应、高灵敏度、可以在线测量等特点,备用来测量飞灰中未燃碳的含量。由于烟气中CO₂气体的存在,碳谱线强度会随CO₂浓度的变化而改变。为了减少CO₂气体对飞灰未燃碳测量结果的影响,提出并设计了具有二级旋风分离器的LIBS测量飞灰未燃碳含量实验系统,飞灰从给粉机流出后通过二级旋风分离器进入测量腔体,脉冲激光经过透镜作用于飞灰样品进而产生等离子体。LIBS系统采用双中心波长光谱仪,可测得飞灰中C,Si,Mg,Fe,Ca和Al等主要元素谱线,同时高分辨率通道可分辨出相邻C和Fe的元素谱线,可以在获得充分的飞灰光谱信息的同时保证了测量的精度。实验结果表明该系统可有效分离和收集飞灰颗粒,减少CO₂气体对测量结果的干扰,为LIBS技术的工程应用提供了更准确的依据。     

缅甸翡翠中铁元素的激光诱导击穿光谱定量检测

采用激光诱导击穿光谱(LIBS)技术定量分析缅甸翡翠中Fe元素的浓度。选择Fe元素的275.57 nm光谱线作为定量分析谱线,选取Si元素的288.17 nm光谱线作为内标谱线,选取12个缅甸翡翠样品作为研究对象,以其中9个样品绘制了传统定标法和内定标法的Fe元素定标曲线,并将定标曲线用于3个检验样品的Fe含量的实际预测。实验结果表明,采用传统定标方法时,定标样品光谱强度的相对标准偏差(RSD)在1.4%～8.3%之间,所建立的Fe元素浓度含量定标曲线的拟合相关系数R2为0.979,使用该方法建立的定标曲线对3个检验样品中Fe元素含量进行测定,最大相对误差为10.6%;而采用内定标法时,定标样品光谱强度的比值(I_Fe/I_Si)的相对标准偏差(RSD)在0.9%～5.7%之间,Fe的拟合相关系数R2达到0.989,样品中Fe元素的测定相对误差均可降低到7%以下。结果证明,利用内定标法定量分析翡翠中Fe的含量比传统定标法相对误差更小,采用LIBS技术结合内定标法更适于缅甸翡翠样品中Fe元素定量分析。     

双脉冲激光诱导光谱结合多变量GA-BP-ANN检测合金钢中C元素

在合金钢众多成分中碳(C)属于微量非金属元素,其含量决定了合金钢的主要力学性能,准确、实时掌握C元素的含量,对合金钢的生产及分类起到关键作用。双脉冲激光诱导击穿光谱(DP-LIBS)是一种可用于在线快速分析合金钢中元素的有效手段,不仅具有实时、样品预处理简单等优点,还能够增强物质的烧蚀度和信号强度,从而提高LIBS技术的检测灵敏度。为了减小基体效应影响,进一步提高LIBS技术对合金钢中微量C元素定量分析的精确性,采用多元素多谱线的修正方法,通过DP-LIBS结合反向传播人工神经网络(BP-ANN),建立多变量GA-BP-ANN定标法。首先在氩气环境对合金钢样品进行DP-LIBS采集,目标C元素选择了谱线强度变化能够体现其含量变化的C 193.09 nm处的原子谱线,同时选取共存元素Fe,Cr,Mn和Si对应的特征谱线,以提供更多的光谱信息,提高C元素定量分析的准确度,共选择15条特征分析谱线,其中Fe元素含量丰富且相对稳定,作为内标元素引入以减小谱线波动;之后通过遗传算法(GA)寻优,对C/Fe,Cr/Fe,Mn/Fe和Si/Fe的谱线强度比进行优化选择;最后将GA选择的多谱线强度比作为BP-ANN网络的输入,输出为目标C元素浓度值,建立多变量GA-BP-ANN定标方法。为比较该方法预测结果的精确性,同时建立传统定标曲线法与以C/Fe为输入的单变量BP-ANN定标方法。利用标准合金钢样品,通过留一法交叉预测C元素含量值,与内标法和单变量BP-ANN定标方法相比,预测样品的平均相对误差分别由14.78%和14.75%减小到8.29%,预测值与真实值之间的决定系数R2分别由0.967 4和0.974 4提升至0.989 3。结果说明了多变量GA-BP-ANN定标法预测的C元素含量更接近于真实含量,证明了该方法用于LIBS检测合金钢中C元素含量的可行性。     

飞灰未燃碳的激光诱导击穿光谱定量分析

为了验证LIBS测量飞灰中碳含量变化的能力,本文将煤粉与飞灰按照一定比例均匀混合,得到24种含碳量不同的样品.在不同延迟时间下进行激光诱导击穿光谱实验,得到温度指标发射强度比I_(Mg1)/I_(Mg2)随延迟时间的增大而减小,纯飞灰样品的发射强度比I_(Mg1)/I_(Mg2)的数值明显大于其他混入煤粉的样品.样品中发射谱线强度比IAl/ISi1随温度指标I_(Mg1)/I_(Mg2)的增大而减小.飞灰样品加入煤粉后,对等离子体的温度变化有明显影响.同时引入多元分析的方法,将样品中C、Al、Mg、Ca、Fe等元素谱线强度与Si元素谱线强度的比值作为多元回归分析的自变量,碳元素浓度作为因变量,建立不同延迟时间下的回归方程.结果表明,采用多元分析的方法进行定量计算,根据回归模型得到的预测值与参考值之间的误差基本在9%以内.     

复混肥中钾含量的激光诱导击穿光谱分析

将激光诱导击穿光谱技术(LIBS)应用于复混肥中的主要营养元素之一钾(K)元素的含量检测.样品中K养分的浓度较高,在等离子体形成过程中容易发生自吸收.通过分析谱线的激发能级、跃迁几率以及自吸收程度,确定最佳分析谱线为钾的原子线404.40 nm.同时为了提高LIBS分析复合肥样品的测量精度,分析了光谱测量稳定性随谱线信号平均次数的变化规律.结果显示,在本实验条件下,一次测量平均100个脉冲所得的光谱信号,其相对标准偏差较小.实验总共分析了9个复合肥样品,其中7个作为定标样品,建立K养分浓度的定标曲线,另外2个作为未知样品,用以检验LIBS分析K养分浓度的测量精确度.研究结果表明,定标曲线的线性拟合度为0.989,检验样品的绝对误差小于0.3%,体现了激光诱导击穿光谱技术快速分析复混肥中钾养分的潜力.     

钢铁中钒、钛元素的激光诱导击穿光谱定量检测

采用激光诱导击穿光谱(LIBS)技术测量钢铁中钒、钛元素的含量。选取V Ⅰ 440.85 nm和Ti Ⅰ 334.19 nm作为定量分析谱线、基体元素谱线Fe Ⅰ 438.35 nm作为内标谱线,分别建立了基本定标法和内定标法的钢铁样品中V和Ti含量的光谱分析定标曲线,并将它们用于检验样品的定量分析。研究表明,V和Ti基本定标曲线的拟合相关系数R2分别为0.987 5和0.990 9,对检验样品中V和Ti元素的测定相对误差最大分别为11.1%和4.0%;而采用内定标法时,V和Ti的拟合相关系数R2分别达到0.995 2和0.992 1,对检测样品中V和Ti元素的测定相对误差均可降低到4.0%以下。结果证明,采用内定标的激光诱导击穿光谱分析方法更适于钢铁样品中钒、钛含量的测定。     

基于多谱线内标法的不规则铜合金样品中 Pb元素成分检测研究

原位分析和在线检测是激光诱导击穿光谱(LIBS)技术的一大优势,但是,在野外环境中,人们无法对样品进行统一预处理,面对各种形态的待测样品如何保证LIBS的检测精度是函待解决的一大难题。提出一种多谱线内定标的方法来解决上述问题,即通过求解多条分析谱线的强度和与内标元素谱线的强度比值来建立定标曲线,进而降低光谱信号波动带来的误差,提高线性相关性和检测精度。实验中以铅黄铜合金样品为例,采用LIBS对厚度不一（最大变化值为±2 mm）的铅黄铜样品中的Pb元素进行了定量检测研究,并分别采用传统定标法和多谱线内定标法对这种不规则样品进行校正和建立定标曲线。实验发现,对于不规则样品,传统定标法的检测精度大大降低,定标曲线没有明显的线性关系。当采用单条谱线的内定标方法时,定标曲线线性相关度大大提高,校正决定系数达到0.724 89。而采用多条谱线内标方法（考虑多条分析谱线的相对强度总和）计算发现,当选取5条Pb谱线（Pb 261.42 nm,Pb 280.20 nm,Pb 368.35 nm,Pb 405.78 nm和Pb 520.14 nm）进行计算时,定标曲线线性拟合度达到0.984 6,由此可见该方法消除了样品不规则所带来的光谱强度波动误差,显著提高了测量精度。虽然继续增加分析谱线数目可以进一步提升线性相关度,但是也会增加计算的复杂度,所以选择合适的分析谱线是十分重要的。此外,通过多谱线内标法也能一定程度上消除基体效应和光谱干扰等影响,是一种简单有效且具备普适性的数据处理方法。当然,该方法也存在一定的局限性（如样品成分分布极不均匀、样品表面极不规则致使激光能量低于击穿阈值等）,不过通过调整和优化检测装置方案（例如增大激光能量、增大聚焦光斑、采用长焦距聚焦透镜等）可以更好的发挥该方法的优势。该研究内容可以为LIBS原位检测和在线检测的应用提供一种新思路。     

激光能量对飞灰颗粒流中未燃碳LIBS检测影响研究

飞灰含碳量是评价锅炉燃烧效率的重要指标之一,对其进行在线测量有助于实时进行燃烧优化调整,从而提高整个机组的经济性和安全性。利用螺杆式给粉机搭建飞灰颗粒流含碳量测量台架,将脉冲激光直接作用于飞灰颗粒流,形成等离子体,利用激光诱导击穿光谱技术测量飞灰颗粒流中的含碳量信息。重点研究了激光能量对飞灰颗粒流中未燃碳有效激发和测量的影响规律。研究结果显示,在40～130 mJ能量的脉冲激光作用下,碳谱线强度随着激光能量的增大线性增强,而其信噪比则先增加后趋于稳定,无效光谱的剔除率则呈下降趋势。本实验条件下,激光能量在90～100 mJ之间,可得到较强的等离子体发射信号和较优的光谱数据利用率。因而激光能量与颗粒流的激发状态、碳元素特征谱线强度等密切相关。合理的激光能量有利于保证飞灰颗粒流的有效稳定激发,并获得具有良好信噪比的等离子体光谱信号。     

复混肥中磷元素的激光诱导击穿光谱多元线性定量分析

复混肥成分的快速、原位检测对化肥的生产过程、产品质量控制具有重要的意义。在化肥企业生产中,实验室进行分析,检测时间长,无法实现线上检测。与复混肥成分现有检测方法相比,激光诱导击穿光谱(LIBS)检测时间只需几分钟、一次测量可完成复混肥成分检测、几乎无需样品预处理,将该技术用于复混肥成分快速、现场检测非常合适。搭建LIBS系统, 激光器(100 mJ, 1 064 nm, 1 Hz)输出的激光束经45°反射镜由水平转为垂直方向,经焦距为40 mm的透镜聚焦至旋转台上的复混肥样品表面,产生激光等离子体。激光器的调Q信号控制光纤光谱仪(Avantes, 195～500 nm)采集信号,设置光谱延迟时间为1.28 μs,采集时间为1.05 ms,最终获取复混肥样品LIBS光谱。20个复混肥样品由安徽徽隆集团提供,磷元素的参考值由企业采用国家标准方法测量。将复混肥样品粉碎过筛取3 g,采用压片机在8 MPa下压制成形。实验中,使用小型风扇吹扫复混肥样品表面,形成稳定气流,每个样品重复测量10次,每次测量平均20个脉冲,以减小样品不均匀性。其中,15个样品用于定标回归模型的建立,五个样品用于检验定标模型的适用性。复混肥是一种成分复杂的混合物,其中氮、磷、钾均以化合物存在。传统的LIBS定量方法是基于待测元素单条谱线强度,未考虑其他元素影响,降低了定量结果的准确性。将LIBS技术和多元线性回归法结合用于分析复混肥中磷元素浓度。选取磷元素的三条特征谱线即213.6,214.9和215.4 nm。磷矿中硅元素含量基本不变,且硅元素在磷的谱线附近存在多条谱线,如212.4,220.8,221.1和221.7 nm。分别采用一元、二元、三元和四元线性回归法建立校准曲线。结果表明,采用P Ⅰ: 214.9 nm谱线强度作自变量建立一元线性回归,LIBS预测值与参考浓度的相关系数仅为0.083,无法满足磷元素的定量分析要求。当采用P Ⅰ: 214.9 nm谱线强度和三条特征谱线之和(P Ⅰ: 213.6, 214.9和215.4 nm)作自变量建立二元线性回归拟合时,相关系数提高到0.856,平均绝对误差由1.32%减小到0.16%。在二元线性回归中引入Si Ⅰ: 212.4 nm谱线强度,建立三元线性回归,相关系数为0.869。为进一步提高磷元素浓度测量的准确性,建立四元线性回归方程,将Si Ⅰ: 212.4,220.8,221.1和221.7 nm谱线强度之和作为自变量加入三元线性回归,相关系数提高到0.980,且15个定标样品的相对误差范围为0.06%～1.31%,而验证样品为0.13%～1.26%,这说明采用四元线性回归定标法可提高复混肥中磷元素浓度测量的准确性。     

Raman and X‐ray diffraction analysis on unburned carbon powder refined from fly ash

The bonding and crystalline structures of oil‐fried fly ash collected from a power plant were analyzed by using Raman spectroscopy and X‐ray diffraction (XRD), respectively. These carbon powders underwent a series of annealing treatment for graphitization and crystallization. In Raman spectra, the refined, unburned carbon contains clearly the D, G and D′ peaks under 2000 or 2700 °C treatment. The Raman spectral line shape of refined, unburned carbon heated at 2700 °C is similar to that of commercial graphite made from graphitization process. In the XRD spectra, the refined, unburned carbon contains (002), (100) and (004) diffraction peaks under heating at 2000 or 2700 °C. The XRD spectral line shape of refined, unburned carbon heated at 2700 °C is similar to that of a commercial graphite bar. The quantitative graphitization level from Raman spectra and crystallization degree from XRD spectra on refined, unburned carbon powders serve as preliminary guide for the qualitative evaluation of these unburned carbon powders. Copyright © 2009 John Wiley & Sons, Ltd.     

Recent progress on laser-induced breakdown spectroscopy for the monitoring of coal quality and unburned carbon in fly ash

Our recent progress on developments of laser-induced breakdown spectroscopy (LIBS) based equipments for on-line monitoring of pulverized coal and unburned carbon (UC) level of fly ash are reviewed. A fully software-controlled LIBS equipment comprising a self-cleaning device for on-line coal quality monitoring in power plants is developed. The system features an automated sampling device, which is capable of elemental (C, Ca, Mg, Ti, Si, H, Al, Fe, S, and organic oxygen) and proximate analysis (Q _ad and A _ad) through optimal data processing methods. An automated prototype LIBS apparatus has been developed for possible application to power plants for on-line analysis of UC level in fly ash. New data processing methods are proposed to correct spectral interference and matrix effects, with the accuracy for UC level analysis estimated to be 0.26%.     

Properties of biomass vs. coal fly ashes deposited in electrostatic precipitator

This paper presents comparative experimental studies of the morphology and elemental composition of fly ash particles from coal- and biomass-fired boilers, deposited in each stage of 3-stage electrostatic precipitators (ESPs). It was shown that fly ash morphology, its physical properties, and the percentage of elements in the fly ash taken from each stage of ESP depend on the kind of fuel. The biomass fly ash contains many irregular large particles, which are pieces of unburned wood. Bulk density of biomass fly ash is on average lower than that of coal fly ash, and drastically decreases in the second and third stages of ESP. The resistivity, measured at electric field of 4 kV/cm, of fly ash from biomass-fired boilers is much lower than that from coal, and can be below 10² Ω m, whereas from coal, except the first stage, varies in the range from 10⁷ to 10¹⁰ Ω m. The low resistivity of coal fly ash in the first stage of ESP results from high carbon content, and of biomass is probably an effect of additional high percentage of potassium, calcium and sodium sulfates. The percentage of Si, Al, Na, Fe, and Ti in fly ash from coal-fired boilers is much higher than from biomass, and in the opposite, the percentage of Mg, K, Ca, Mn, Mo, S, Cl, and P in biomass ash exceeds that in coal fly ash. Potential detrimental effects of biomass combustion products (salts, acids, tar) leaving the boiler on the construction elements of the electrostatic precipitator, including electrodes and HV insulators have been discussed in this paper. It was concluded that the long-term effects of biomass co-firing on the electrostatic precipitator performance, including the collection efficiency, have not been sufficiently studied in the literature and these issues require further detailed investigations.     

阻尼最小二乘法用于激光诱导击穿光谱重叠特征谱线分离提取

近年来,激光诱导击穿广谱技术发展迅速。作为一种用于物质成分探测的新技术,它具有简单、快速、无需复杂样品制备、多种元素同时检测等优点,可实现待测样品物质成分现场、在线的检测,在很多领域都极具应用前景。激光诱导击穿光谱特征谱线的分离拟合提取是光谱特征识别与后续元素浓度定量反演研究的基础。为实现激光诱导击穿光谱重叠特征谱线的有效分离拟合提取,采用阻尼最小二乘法,分析并确定了迭代前的初始拟合参数值,实现了在重叠特征谱线情况下对某火力发电厂粉煤灰中的铬元素特征谱线的分离提取。阻尼最小二乘法基于高斯-牛顿迭代,在迭代步长中引入阻尼因子,在迭代的过程中根据每一步迭代后所反馈的信息动态的调整迭代步长,从而有效防止了迭代的发散,保证了迭代的快速收敛,最终使得元素特征谱线拟合提取的效果更佳、所得到的特征谱线强度值更准确。分别采用阻尼最小二乘法和最小二乘法对不同浓度的样品中铬元素特征谱线进行分离拟合提取并给出特征谱线的强度值,作出特征谱线强度值关于元素浓度的定标曲线并对比两种方法所得结果的线性相关性。结果表明,阻尼最小二乘法所得结果的线性相关性更高,该方法稳定、可靠,适用于激光诱导击穿光谱重叠特征谱线的分离拟合提取。     

Correction and analysis of lead content in soil by laser-induced breakdown spectroscopy

The laser-induced breakdown spectroscopy is used to analyze the lead content in soils. The analyzed spectral line profile is fitted by Lorentzian function for determining the background and the full-width at half-maximum （FWHM） intensity of spectral line. A self-absorption correction model based on the information of spectral broadening is introduced to calculate the true value of spectral line intensity, which refers to the elemental concentration. The results show that the background intensity obtained by spectral profile fitting is very effective and important due to removing the interference of spectral broadening, and a better precision of calibration analysis is acquired by correcting the self-absorption effect.     

Investigation of unburned carbon particles in fly ash by means of laser light scattering

A new optical method to determine the percentage of unburned carbon particles in fly ash from combustion of pulverized coal has been developed. The technique exploits the different properties of particles of ash and coal in the elastic scattering of polarized light.     

Review of methodological and experimental LIBS techniques for coal analysis and their application in power plants in China

Laser-induced breakdown spectroscopy (LIBS) is an emerging analytical spectroscopy technique. This review presents the main recent developments in China regarding the implementation of LIBS for coal analysis. The paper mainly focuses on the progress of the past few years in the fundamentals, data pretreatment, calibration model, and experimental issues of LIBS and its application to coal analysis. Many important domestic studies focusing on coal quality analysis have been conducted. For example, a proposed novel hybrid quantification model can provide more reproducible quantitative analytical results; the model obtained the average absolute errors (AREs) of 0.42%, 0.05%, 0.07%, and 0.17% for carbon, hydrogen, volatiles, and ash, respectively, and a heat value of 0.07 MJ/kg. Atomic/ionic emission lines and molecular bands, such as CN and C₂, have been employed to generate more accurate analysis results, achieving an ARE of 0.26% and a 0.16% limit of detection (LOD) for the prediction of unburned carbon in fly ashes. Both laboratory and on-line LIBS apparatuses have been developed for field application in coal-fired power plants. We consider that both the accuracy and the repeatability of the elemental and proximate analysis of coal have increased significantly and further efforts will be devoted to realizing large-scale commercialization of coal quality analyzer in China.     

强度比定标法分析激光诱导击穿碳谱线

 利用激光诱导击穿光谱技术,使样品在大气常压环境下被击穿形成等离子体,探测等离子体发射信号。选择混合样品所含的基体元素硅作为内标元素,分别根据碳谱线峰值强度、分析线和内标线峰值强度比建立不同的定标曲线。对两种定标曲线的拟合度、测量重复性以及定量分析结果准确度进行了研究。研究结果表明:强度比定标法在一定程度上可以提高定标曲线的拟合度和测量重复性,减小强度比定标法定量分析结果的误差,提高测量准确度。