差分吸收光谱法在线测量排放烟气浓度研究

介绍了差分吸收光谱(DOAS)在线测量系统,分析了DOAS的光谱处理方法.研究了SO2气体浓度的DOAS测量方法,可以实现排放烟气中SO2的在线测量.DOAS法利用数学方法将吸收光谱分解成快变和慢变部分,他利用快变部分计算气体成分的浓度,这使得烟尘干扰和光源强度变化不影响烟气浓度测量精度.DOAS法用线测量代替点测量,可获得区域内更具有代表性的数据,能更准确的反映烟气排放情况;可同时对多种污染物的进行定性、定量分析;是非接触性测量,无需采样.     

基于多方法集成的烟气、烟尘排放监测系统

根据SO2和NOx以及烟尘分别在不同光谱波段具有吸收和散射特性的特点,对同一测量光谱分别用差分吸收光谱法(DOAS)和多波长消光法进行数据处理,并辅之互相关法,可同时监测SO2、NOx和烟尘的浓度、烟尘粒度以及总排放量。基于这些方法,研制了一套直接在线烟气连续监测系统(CEMS)。在一采暖锅炉上成功地进行了不同运行工况下现场较长时间连续监测。     

烟气在线监测系统及思考

固定污染源排放的烟气会对环境造成污染,对其进行科学监测至关重要。本文介绍了现有的烟气在线监测系统,包括空气质量自动监测系统、烟气排放连续监测系统、差分光学吸收光谱法在线连续监测系统、物联网下无线传感器网络技术在线监测系统等,介绍了每个系统的组成、技术特点、监测方法、实际应用和发展方向,并从量值溯源和远程校准两个方面对烟气在线监测系统与计量系统的关系进行了阐述。     

基于紫外差分吸收光谱的高温便携式 气体分析仪的设计

针对超低排放的烟气监测,研制了基于紫外差分吸收光谱技术的便携式高温烟气分析仪,阐述了分析仪的测量原理以及仪器的机械结构、光学、温控设计,采用不同浓度的SO2和NOX标准气体在不同环境条件下对该仪器进行测试,结果表明仪器的性能指标可达到污染源环保管理和环境污染应急监测的要求,具有良好的环境适应性。基于该仪器的硬件平台,未来通过扩展设计和应用开发升级也可应用于大气监测领域的走航监测。     

热电厂连续监测系统CEMS烟气污染物测量不确定度研究

烟气排放连续监测系统(CEMS)已经广泛运用于热电联产机组烟气污染物排放监测中,并且测试数据实时上传到生态环境部门。为了评估某热电厂CEMS系统监测数据的准确度和可信度,分析了该系统中影响烟气污染物测量不确定度分量因素,主要包括零点漂移、量程漂移、示值误差、测量误差、标准气体组分浓度和测量重复性。结果表明当包含因子 k=2,置信概率为95%时,SO2、NO和NO2的扩展不确定度分别为2.28mg/m³、3.50mg/m³和0.50mg/m³。由于参比法与CEMS对烟气监测的采样方式不同,使测量误差引入的不确定度分量最大。     

紫外烟气连续监测系统在超低排放中的应用

介绍一种基于紫外差分吸收光谱(DOAS)技术,高温全程伴热的超低量程烟气连续监测系统(CEMS-2000L)。其技术指标达到:量程100 mg/m3,线性误差≤±1%FS,24 h零点漂移、量程漂移≤±2%FS,响应时间110 s。将该系统应用于超低排放污染源现场,并且与非分散红外仪表进行比对测试。比对结果显示:测量值与参比方法的绝对误差小于3 mg/m~3,表明高温抽取式紫外DOAS技术适用于固定污染源超低排放的检测需求。     

烟气排放连续监测系统(CEMS)采样技术及PM2.5监测问题的研究

烟气排放连续监测系统(CEMS)用于对大气固定污染源排放的烟尘、气态污染物进行排放浓度以及其它烟气参数的连续监测。简要介绍了燃煤产生的颗粒物,尤其是PM2.5给人体造成的危害,着重分析了CEMS系统的采样方法和PM2.5的重量测定,比较其各自的特点,最后,对有关现场校准的问题及PM2.5监测的问题进行探讨。     

关于工况排放测试系统中定容取样系统气体流量校准方法及量值溯源探讨

正一、概述工况排放测试系统主要用于汽车、摩托车等机动车辆在规定的工况行驶状态下,排放出HC、CO、CO2和NO等有害气体成分及含量的测试设备。鉴于国家尚无工况排放测试系统相关的计量检定规程及校准方法,根据国内外行业规范、工况排放测试系统的工作原理以及工况排放测试系统校准方法,以及GB14622-2016《摩托车污染物排放限值及测量方法(中国第四阶段)》,可对工况排放测试系统进行线性     

固定污染源烟气汞排放连续监测系统最新进展

正据统计,"十二五"末期国内燃煤电厂有超过30家配备了进口的汞排放在线监测装置,开展污染源烟气汞排放试点连续监测。固定污染源烟气汞排放连续监测系统(Hg-CEMS)除了具备常规烟气自动监控系统的采样和预处理单元、分析测量单元、辅助设备单元外,还需要配置独立的汞标准气体发生校准单元,即     

烟气排放连续监测系统流速误差影响分析

烟气排放连续监测系统(CEMS)由颗粒物CEMS、气态污染物CEMS、烟气参数测定子系统组成。烟气流速准确与否直接关系颗粒物和气态污染物排放率及其总量监测。文章分析几种烟气流量计原理,找出河南省应用最多的皮托管式流量计流速误差影响因素,并针对各影响因素做以误差影响分析,依据分析结果给出了CEMS流速误差日常校准和检定的建议。     

Numerical analysis and estimation of the statistical error of differential optical absorption spectroscopy measurements with least-squares methods

Differential optical absorption spectroscopy (DOAS) has become a widely used method to measure trace gases in the atmosphere. Their concentration is retrieved by a numerical analysis of the atmospheric absorption spectra, which often are a combination of overlapping absorption structures of several trace gases. A new analysis procedure was developed, modeling atmospheric spectra with the absorption structures of the individual trace gases, to determine their concentrations. The procedure also corrects differences in the wavelength-pixel mapping of these spectra. A new method to estimate the error of the concentrations considers the uncertainty of this correction and the influence of random residual structures in the absorption spectra.     

Tomographic multiaxis-differential optical absorption spectroscopy observations of Sun-illuminated targets: a technique providing well-defined absorption paths in the boundary layer

A novel experimental procedure to measure the near-surface distribution of atmospheric trace gases by using passive multiaxis differential absorption optical spectroscopy (MAX-DOAS) is proposed. The procedure consists of pointing the receiving telescope of the spectrometer to nonreflecting surfaces or to bright targets placed at known distances from the measuring device, which are illuminated by sunlight. We show that the partial trace gas absorptions between the top of the atmosphere and the target can be easily removed from the measured total absorption. Thus it is possible to derive the average concentration of trace gases such as NO(2), HCHO, SO(2), H(2)O, Glyoxal, BrO, and others along the line of sight between the instrument and the target similar to the well-known long-path DOAS observations (but with much less expense). If tomographic arrangements are used, even two- or three-dimensional trace gas distributions can be retrieved. The basic assumptions of the proposed method are confirmed by test measurements taken across the city of Heidelberg.     

Alternative method for concentration retrieval in differential optical absorption spectroscopy atmospheric-gas pollutant measurements

Differential optical absorption spectroscopy is a widely used technique for open-column atmospheric-gas pollution monitoring. The concentration retrieval is based on the fitting of the measured differential absorbance through the Lambert-Beer law. We present an alternative method for calculating the gas concentration on the basis of the proportionality between differential absorbance and differential absorption cross section of the gas under study. The method can be used on its own for single-component analysis or as a complement to the standard technique in multicomponent cases. The performance of the method for the case of cross interference between two gases is analyzed. The procedure can be used with differential absorption cross sections measured in the laboratory or taken from the literature. In addition, the method provides a criterion to discriminate against different species having absorption features in the same wavelength range.     

Development of Fourier transform spectrometry for UV-visible differential optical absorption spectroscopy measurements of tropospheric minor constituents

Concentration measurements of trace gases in the atmosphere require the use of highly sensitive and precise techniques. The UV-visible differential optical absorption spectroscopy technique is one that is heavily used for tropospheric measurements. To assess the advantages and drawbacks of using a Fourier transform spectrometer, we built a differential optical absorption spectroscopy optical setup based on a Bruker IFS 120M spectrometer. The characteristics and the capabilities of this setup have been studied and compared with those of the more conventional grating-based instruments. Two of the main advantages of the Fourier transform spectrometer are (1) the existence of a reproducible and precise wave-number scale, which greatly simplifies the algorithms used to analyze the atmospheric spectra, and (2) the possibility of recording large spectral regions at relatively high resolution, enabling the simultaneous detection of numerous chemical species with better discriminating properties. The main drawback, on the other hand, is due to the fact that a Fourier transform spectrometer is a scanning device for which the scanning time is small compared with the total measurement time. It does not have the signal integration capabilities of the CCD or photodiode array-based grating spectrographs. The Fourier transform spectrometer therefore needs fairly large amounts of light and is limited to short to medium absorption path lengths when working in the UV.     

Operator representation as a new differential optical absorption spectroscopy formalism

UV-visible absorption spectroscopy with extraterrestrial light sources is a widely used technique for the measurement of stratospheric and tropospheric trace gases. We focus on differential optical absorption spectroscopy (DOAS) and present an operator notation as a new formalism to describe the different processes in the atmosphere and the simplifying assumptions that compose the advantage of DOAS. This formalism provides tools to classify and reduce possible error sources of DOAS applications.     

Improvement of differential optical absorption spectroscopy with a multichannel scanning technique

Differential optical absorption spectroscopy (DOAS) of atmospheric trace gases requires the detection of optical densities below 0.1%. Photodiode arrays are used more and more as detectors for DOAS because they allow one to record larger spectral intervals simultaneously. This type of optical multichannel analyzer (OMA), however, shows sensitivity differences among the individual photodiodes (pixels), which are of the order of 1%. To correct for this a sensitivity reference spectrum is usually recorded separately from the trace-gas measurements. Because of atmospheric turbulence the illumination of the detector while an atmospheric absorption spectrum is being recorded is different from the conditions during the reference measurement. As a result the sensitivity patterns do not exactly match, and the corrected spectra still show a residual structure that is due to the sensitivity difference. This effect usually limits the detection of optical densities to approximately 3 × 10(-4). A new method for the removal of the sensitivity pattern is presented in this paper: Scanning the spectrometer by small wavelength increments after each readout of the OMA allows one to separate the OMA-fixed pattern and the wavelength-fixed structures (absorption lines). The properties of the new method and its applicability are demonstrated with simulated spectra. Finally, first atmospheric measurements with a laser long-path instrument demonstrate a detection limit of 3 × 10(-5) of a DOAS experiment.     

Multiwavelength discrimination and measurements of a two-gas mixture by use of a broadly tunable mid-infrared semiconductor laser

Spectroscopic detection of gases can be achieved by measuring a few species-specific absorption lines, requiring very accurate wavelength control. Alternatively, it can be achieved by using many wavelengths spread over a wide range; each wavelength need not be optimal spectroscopically, but all collectively form a unique fingerprint for the species of interest. Statistical regression can be used to quantify their concentrations. An experimental evaluation of this concept involved using a 3.1 microm broadly tunable Sb-based mid-IR laser to discriminate and measure mixtures of acetylene and water vapor with absorption spectral overlaps. As many as 30 wavelengths from approximately 3200 to approximately 3280 cm-1 were used to measure 5 x 5 combinations of the two-gas concentration. Statistical analysis of the results validates the concept. Each gas concentration was consistently and reliably measured without any problem of interference from the other. In addition, the method was sufficiently sensitivite to detect unusual discrepancies by use of statistical analysis. Optimization of the system's detection capability and its receiver-operating characteristics is demonstrated. The results suggest that the statistical multiwavelength broadband approach to detection of gas mixture can be a highly effective alternative to species-specific single-line spectroscopy.     

Simultaneous and continuous multiple wavelength absorption spectroscopy on nanoliter volumes based on frequency-division multiplexing fiber-loop cavity ring-down spectroscopy

We demonstrate a method for measuring optical loss simultaneously at multiple wavelengths with cavity ring-down spectroscopy (CRD). Phase-shift CRD spectroscopy is used to obtain the absorption of a sample from the phase lag of intensity modulated light that is entering and exiting an optical cavity. We performed dual-wavelength detection by using two different laser light sources and frequency-division multiplexing. Each wavelength is modulated at a separate frequency, and a broadband detector records the total signal. This signal is then demodulated by lock-in amplifiers at the corresponding two frequencies allowing us to obtain the phase-shift and therefore the optical loss at several wavelengths simultaneously without the use of a dispersive element. In applying this method to fiber-loop cavity ring-down spectroscopy, we achieve detection at low micromolar concentrations in a 100 nL liquid volume. Measurements at two wavelengths (405 and 810 nm) were performed simultaneously on two dyes each absorbing at mainly one of the wavelengths. The respective concentrations could be quantified independently in pure samples as well as in mixtures. No crosstalk between the two channels was observed, and a minimal detectable absorbance of 0.02 cm(-1) was achieved at 405 nm.     

Wavefront error measurement of high-numerical-aperture optics with a Shack-Hartmann sensor and a point source

We developed a new, to the best of our knowledge, test method to measure the wavefront error of the high-NA optics that is used to read the information on the high-capacity optical data storage devices. The main components are a pinhole point source and a Shack-Hartmann sensor. A pinhole generates the high-NA reference spherical wave, and a Shack-Hartmann sensor constructs the wavefront error of the target optics. Due to simplicity of the setup, it is easy to use several different wavelengths without significant changes of the optical elements in the test setup. To reduce the systematic errors in the system, a simple calibration method was developed. In this manner, we could measure the wavefront error of the NA 0.9 objective with the repeatability of 0.003 lambda rms (lambda = 632.8 nm) and the accuracy of 0.01 lambda rms.     

Multipass optical absorption spectroscopy: a fast-scanning laser spectrometer for the in situ determination of atmospheric trace-gas components, in particular OH

The optical design of an absorption spectrometer for in situ measurements of atmospheric trace gases is reported. The light source is a rapidly tuned and power-stabilized dye-ring laser, which is frequency doubled by an intracavity BBO crystal. The second harmonic and the fundamental are used simultaneously for measurement of OH, SO(2), CH(2)O, and naphthalene in the UV and of NO(2) in the visible. The 1.2-km absorption path is folded within a 6-m White-cell-type multiple-reflection system with an open-path setup. The absorption sensitivity of the spectrometer is better than 1 part in 10(-5) under tropospheric conditions (integration time 1 min., signal-to-noise ratio 1).