紫外吸收光谱法在线测量SO3的实验研究

基于紫外吸收光谱法对SO₃的在线测量进行了实验研究,搭建了SO3气体发生系统。为提高检测精度,探究了去除测量过程中的各种干扰因素。SO₃与SO₂的特征吸收波段重叠严重,通过合理选择特征吸收波段和光谱反演策略最大程度地去除SO₂对SO₃测量的影响。研究中采用标准曲线法结合单波长法、双波长法和积分光谱法建立了标准曲线。结果表明:积分光谱法的测量误差最小,可优先应用于SO3排放的在线光谱计量分析。     

基于MIC和MPA-KELM的脱硫出口SO2浓度预测

建立脱硫出口SO₂浓度预测模型是实现脱硫系统经济运行的基础。针对这一问题,提出了基于最大信息系数(MIC)的变量选择方法和基于海洋捕食算法(MPA)优化核极限学习机(KELM)的脱硫出口SO₂浓度预测模型。首先,采用机理分析法筛选影响出口SO₂浓度的变量,提出循环浆液综合流量表达方法,便于描述浆液循环泵组合的影响特性;在此基础上,通过基于最大信息系数的变量选择算法确定模型输入变量;运用MPA对KELM的正则系数C和核参数S进行寻优,建立MPA-KELM的出口SO₂浓度预测模型;最后,利用电厂运行数据进行仿真实验。实验结果表明,所建立出口SO₂浓度预测模型的均方误差、平均绝对百分比误差分别为1.236 66 mg/m³和4.987 6%,预测精度高,能够为脱硫系统出口SO₂的现场优化控制提供技术支持。     

基于渗透管法制作汞标气

为了实现在线大气汞分析仪的自动标定,本文选用商用的汞渗透管,制作汞标气。我们基于渗透管法设计了一套汞标气发生器装置,主要装置有渗透管、U型管、恒温箱、低压汞灯等。同时为了提高汞标气的精度,我们总结了实验过程中的影响因素,其中渗透率和恒温环境是主要影响因素。     

电气设备中保护气体监测用SO2F2气体标准物质研制

介绍了钢瓶装氦气中氟化硫酰（SO₂F₂）气体标准物质的研制过程。标准混合气是通过将SO₂F₂和氦气充装到钢瓶中制备而成,研究了气瓶内压力和保存时间对混合气稳定性的影响。对混合气配制的一致性进行了考察,并对引入的不确定度进行了评估,由结果可以看出,每个摩尔分数点混合气的量值一致性均较好。通过对称量法配气与稳定性导致的不确定度的评价,结果显示利用称量法制备的氦气中SO₂F₂气体标准物质在6个月内的稳定性良好,其相对扩展不确定度不大于2%。     

电子特气中痕量水溶性杂质的捕集方法研究

配制系列离子浓度标准溶液,使用离子色谱绘制了液相NH⁺₄的校准曲线,作为气体吸收实验的定量依据。使用自制气体吸收装置和标准气体进行气体吸收实验,确定了吸收液种类、吸收瓶材质。通过正交实验考察了吸收速率、吸收时间、吸收液体积和吸收瓶规格4个参数对捕集效率的影响,选出最优参数。通过气体稀释仪,绘制了不同浓度下氢中NH⁺₄的气体响应校准曲线,线性良好。确定了气体吸收的检出限,远高于市场检测需求。所进行的吸收参数等的考察为我国集成电路基础材料检测的发展提供了有利的技术支撑。     

基于小波优化EEMD的二氧化硫检测

为解决检测SO₂时系统接收到的荧光信号微弱、易被噪声淹没的问题,提出了小波优化总体经验模态分解(EEMD)的方法对SO₂荧光信号进行去噪。搭建了SO₂紫外荧光检测系统对SO₂浓度进行检测,检测的平均相对误差为0.0011, SO2浓度与荧光强度的线性相关系数为0.9787。利用小波优化EEMD去噪方法对SO₂荧光信号去噪,得到的信噪比为224.7958,均方误差为1.01×10^-7,波形相似系数为0.9973,SO2浓度与荧光强度的线性相关系数为0.9936。相比于EEMD和小波去噪方法,小波优化的EEMD去噪方法对SO2荧光信号的去噪效果更好,能够达到理想的去噪效果。     

基于RBF神经网络的生物质电站高温气体CO2浓度测量方法

电站气体浓度测量对实现燃烧优化、提高燃烧效率和火焰品质、减少污染物排放具有重要意义。以CO₂气体为例进行研究,基于近红外波段可调谐激光吸收层析成像技术,提出了基于径向基(radial basis function, RBF)神经网络的高温气体CO₂浓度测量方法。通过实验获取不同浓度下的CO₂吸收可调谐激光光谱信号,计算CO₂吸收谱线和原始信号的差值,提取出描述该差异性的统计特征参数作为RBF神经网络的输入,CO₂浓度作为RBF神经网络的输出,建立了基于RBF神经网络的高温气体CO₂浓度测量仿真模型,通过仿真实例验证了该方法的有效性和正确性。与GRNN神经网络对比分析表明:RBF神经网络法可以有效提高CO₂浓度测量精度,为生物质发电高温气体计量提供理论依据。     

燃煤电厂烟气中SO3的生成、危害、测试及排放特征研究

燃煤电厂烟气中SO₃等非常规污染物的排放尚未得到有效控制,其危害主要表现在低温腐蚀、设备堵塞和环境污染等,主要来源于煤的燃烧。对中国200种煤种基硫含量（S_ar）进行统计分析,其范围在0.11%~3.47%,平均值为0.82%;SO₃采样方法主要有控制冷凝法、异丙醇吸收法,将2种方法耦合使用,可大幅提高SO₃的捕集率,提高测试数据的准确性;基于现场实测及文献调研,对现有燃煤电厂的SO₃排放特征进行表征。结果可为后续燃煤电厂SO₃排放控制提供借鉴。     

光谱共焦传感器多参数高准确度校准

针对高准确度光谱共焦传感器缺乏相应校准装置及方法的问题,提出了一种基于激光干涉测量的校准方法,并研制了相应的校准装置。一方面,提出了一种波长倍数间隔测量法,通过位移反馈控制将位移间隔设置为激光波长的整数倍,以减小激光干涉仪非线性误差对测量的影响;另一方面,提出了测点修正算法,消除了受检点处位移标准值因校准装置定位准确度限制不重合对测量的影响。实验结果表明：在0～100μm的测量范围内,示值误差为±23 nm,重复性为5 nm,示值误差测量结果的扩展不确定度U₂=7.0 nm(k=2)。构建的校准装置在0～50 mm的测量范围内的示值误差测量结果不确定度为U₁=3.0 nm+2×10^-7L(k=2)。     

作为标准物质的二氧化硫和二氧化氮渗透管的研制(英文)

本文介绍近年来中国计量科学研究院作为标准物质二氧化硫和二氧化氮渗透管的研制工作。简要叙述了渗透管的工作原理和用重量法校准渗透率的方法,讨论了影响渗透率的各种因素、温度改变后渗透率达到平衡的时间以及渗透管的长期稳定性。实验结果表明,这两种渗透管渗透率测定的不确定度都在±1％以内(95％置信度),并经审定作为中国的标准物质。     

Reducing the Uncertainty of Industrial Trace Humidity Generators through NIST Permeation-Tube Calibration

Permeation-tube moisture generators (PTGs) are commonly used by the semiconductor industry as transfer standards for the calibration of hygrometer systems measuring trace amounts of water vapor in gases (water vapor mole fractions typically below 1 × 10⁻⁶). They are relatively simple devices that generate a steady stream of humidified gas by diluting water vapor delivered at a constant rate from a permeable capsule with precisely metered purified gas, usually nitrogen. Here a new calibration service enabling the measurement of PTG permeation rates directly in terms of NIST primary standards of trace humidity generation is described. Rather than using commonly employed gravimetric methods for permeation-tube calibration, the method applied here links the permeation rate of the permeation tube to the thermodynamic properties of ice. Using a hygrometer based on cavity ringdown spectroscopy, we compare the water vapor concentrations produced by the NIST low frost-point generator (LFPG) and a specially constructed PTG containing the permeation tube undergoing calibration. A least squares fit of the data determines the permeation rate of the tube under test. We describe the calibration system, experimental procedure and present sample calibration data. The expanded relative uncertainty of NIST permeation-tube calibrations is 1.8% with a coverage factor k = 2, dominated by the Type A uncertainties.     

烟道截面面积校准装置模型研究及不确定度评定

为了保证基于速度面积法烟道流量测量的准确性,需要准确测量出烟道截面面积。研发了一套烟道截面面积在线校准装置,能准确测量烟道内部几何尺寸,进而计算截面面积。讨论了基于随机抽样一致性截面面积拟合算法以及基于最小二乘法截面面积算法拟合计算的拟合特性,对比并优化后的拟合模型测量平均值的最大偏差为0.02%,装置测量重复性为0.013%。同时对装置的测量不确定进行评定,校准装置相对扩展不确定度为0.17%(k=2)。     

Dual Differential Absorption Lidar for the Measurement of Atmospheric SO(2) of the Order of Parts in 10(9)

Vertical concentration profiles of atmospheric SO(2) of the order of parts in 10(9) (ppb) were measured by a multiwavelength differential absorption lidar system. The error that was due to O(3) and aerosols was successfully reduced by a three-wavelength dual differential absorption lidar (DIAL), and a SO(2) concentration of 1.2 ppb for 2400-3000-m altitude was obtained with 300-m range resolution. The measurement error in dual DIAL was estimated to be <1.1 ppb when several factors were considered. The influence of O(3) on SO(2) measurement error was experimentally evaluated from simultaneous measurements of atmospheric SO(2) and O(3) by two conventional DIAL pairs, each using two wavelengths.     

Trace atmospheric SO2 measurement by multiwavelength curve-fitting and wavelength-optimized dual differential absorption lidar

We present a new differential absorption lidar (DIAL) method for atmospheric trace SO2 using multi-wavelength curve fitting. With this method we use five wavelengths around a SO2 absorption peak and obtain SO2 and O3 concentrations by fitting their absorption cross sections to measured DIAL and null results. A SO, concentration of 6 parts in 10(9) (ppb) was obtained for an altitude of 1050 m with 150-m range resolution. In addition, we optimized the wavelengths for dual-DIAL SO2 measurement and demonstrated a high sensitivity of <0.5 ppb with 300-m range resolution. Comparison of these two methods is also presented.     

Direct determination of methylmercury and inorganic mercury in biological materials by solid sampling-electrothermal vaporization-inductively coupled plasma-isotope dilution-mass spectrometry

This paper reports on the use of solid sampling-electrothermal vaporization-inductively coupled plasma mass spectrometry (SS-EIV-ICPMS) for the direct and simultaneous determination of methylmercury and inorganic mercury in biological materials. The main advantage of this fast and sensitive method is that no sample preparation is required. In this way, the sample throughput can be considerably increased, problems of contamination and analyte losses are kept to a minimum and, even more important, the original chemical form of the different analyte species in the solid samples is preserved. To achieve this goal, a solid sample is inserted into a graphite furnace of the boat-in-tube type and is subsequently submitted to an appropriate temperature program, leading to the separate vaporization of methylmercury and inorganic mercury, which are transported into the ICP by means of an argon carrier gas. The separation was accomplished within 75 s. For the quantification of the two peaks, species-unspecific isotope dilution was used. For this purpose, a stable flow of argon loaded with gaseous Hg isotopically enriched in 200Hg was generated using a permeation tube that was constructed in-house. Its emission rate was determined by collecting the mercury released during a given time interval on a gold-coated silica absorber, after which the amount collected was released by heating of the absorber and determined by cold vapor atomic absorption spectrometry (CVAAS) and cold vapor atomic fluorescence spectrometry (CVAFS). A reference material from the Canadian National Research Council (NRC) (TORT-2) was used to assess the accuracy of the method. For the application of the method to samples with diverse mercury contents, the spike/sample ratio can be optimized by varying the emission rate of the permeation tube simply by adapting its temperature. To prove the feasibility of this approach, two reference materials (BCR 463 and DORM-2) with a methylmercury content more than 10 times higher than that of TORT-2 were also analyzed. The detection limits obtained for 1 mg of sample (2 ng g(-1) and 6 ng g(-1) for methylmercury and inorganic mercury, respectively) were found to be sufficiently low for this kind of application and are competitive when compared to other techniques.     

EvaluatingWater Vapor Permeance Measurement Techniques for Highly Permeable Membranes

The cup method and dynamic moisture permeation cell (DMPC) method are two common techniques used to determine the water vapor permeation properties of a membrane. Often, ignoring the resistance of boundary air layers to the transport of water vapor results in the water vapor permeance of the membrane being underestimated in practical tests. The measurement errors are higher with highly permeable membranes. In this study, the two methods were simulated using COMSOL Multiphysics platform and the extent of the error was evaluated. Initial results showed that the error is equally high in both methods. With the correction for the still air gap, the cup method produces a relatively reduced error. In the DMPC method, reducing the error caused by the boundary air layer by increasing the sweep speed can produce higher instrument error. Highly accurate and precise instrument is needed for DMPC method; however, its error is still higher than that in the cup method. Simulations also show that lowering the test pressure is favorable to both methods.     

A Predictive Instrument for Sensitive and Expedited Measurement of Ultra-Barrier Permeation

The reliable operation of flexible display devices poses a significant engineering challenge regarding the metrology of high barriers against water vapor. No reliable results have been reported in the range of 10^–6 g∙(m²∙d)⁻¹, and there is no standard ultra-barrier for calibration. To detect trace amount of water vapor permeation through an ultra-barrier with extremely high sensitivity and a greatly reduced test period, a predictive instrument was developed by integrating permeation models into high-sensitivity mass spectrometry measurement based on dynamic accumulation, detection, and evacuation of the permeant. Detection reliability was ensured by means of calibration using a standard polymer sample. After calibration, the lower detection limit for water vapor permeation is in the range of 10^–7 g∙(m²∙d)⁻¹, which satisfies the ultra-barrier requirement. Predictive permeation models were developed and evaluated using experimental data so that the steady-state permeation rate can be forecasted from non-steady-state results, thus enabling effective measurement of ultra-barrier permeation within a significantly shorter test period.     

基于高温还原及差分吸收光谱监测烟气汞的实验研究

高温还原法在不需要催化剂的条件下可将烟气排放中的二价汞转化为零价汞,便于进行烟气总汞的监测。运用差分吸收光谱法（DOAS）反演出烟气汞浓度,与没有加高温装置的测量结果作对比,验证高温设备的适用性,并配比不同浓度的零价汞和二价汞进行混合实验。在传统的DOAS算法基础上,研究遗传算法、傅里叶变换滤波及积分面积法对烟气汞浓度的影响。实验结果表明:传统算法具有偶然性,整体误差大;傅里叶变换反演出的浓度误差较大;积分面积法较遗传算法误差偏低,整体波动也小,反演出的偏差最小为0.55%,适合用于反演低浓度排放的烟气汞测量。     

驻波管测试仪测量金属橡胶吸声性能误差分析

驻波管测试仪是用于测量材料吸声性能的专用仪器，利用该仪器对金属橡胶吸声性能进行测量，使测量结果满足金属橡胶吸声性能实验研究的精度要求，且便于材料实验结果的误差分析，需对驻波管测试仪进行检测和调试。借助于吸声性能参数的理论计算公式，分析了AWA6122A型驻波管测试仪的主要误差来源，分别检测了各主要误差源的误差大小，确定了提高测量精度的方法，为金属橡胶吸声性能的实验研究提供基础，也为同类仪器的检测提供了方法。     

烟气排放污染物(SO2)在线监测系统

紫外 可见差分吸收光谱法 (DOAS)是一种可用于在线式烟气排放污染物自动监测的新型方法 ,它在不改变被测试样成分的前提下 ,可以同时对多种气体进行连续测量。对获得的吸收光谱数据由计算机处理 ,可实时记录烟气中各种污染物的含量 ,并对未知成分的气体进行判断。介绍了基于这种测量方法的测试系统的结构、工作原理 ,并利用所建立的测试系统进行了实验研究。测试结果表明 :采用差分吸收光谱法所测得的SO2 浓度在满量程范围内偏差均≤± 1 5 % ,完全可以满足烟气排放污染物 (SO2 )连续在线监测的要求