WO2012123124A1 - Procédé et appareil de mesure pour la détermination d'atomes et de molécules dans des échantillons d'analyse - Google Patents

Procédé et appareil de mesure pour la détermination d'atomes et de molécules dans des échantillons d'analyse Download PDF

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Publication number
WO2012123124A1
WO2012123124A1 PCT/EP2012/001167 EP2012001167W WO2012123124A1 WO 2012123124 A1 WO2012123124 A1 WO 2012123124A1 EP 2012001167 W EP2012001167 W EP 2012001167W WO 2012123124 A1 WO2012123124 A1 WO 2012123124A1
Authority
WO
WIPO (PCT)
Prior art keywords
simultaneous
analyte
mercury
wavelength
narrow
Prior art date
Application number
PCT/EP2012/001167
Other languages
German (de)
English (en)
Inventor
Christian Buck
Original Assignee
Christian Buck
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Christian Buck filed Critical Christian Buck
Priority to EP12715817.8A priority Critical patent/EP2686666A1/fr
Publication of WO2012123124A1 publication Critical patent/WO2012123124A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
    • G01N21/3151—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths using two sources of radiation of different wavelengths
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/3103—Atomic absorption analysis
    • G01N2021/3118—Commutating sources, e.g. line source/broad source, chopping for comparison of broad/narrow regimes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N2021/3125—Measuring the absorption by excited molecules
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01—Arrangements or apparatus for facilitating the optical investigation
    • G01N21/03—Cuvette constructions
    • G01N21/031—Multipass arrangements
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/12—Circuits of general importance; Signal processing
    • G01N2201/129—Using chemometrical methods

Definitions

  • the invention relates to a method and instrument for the qualitative and quantitative determination of analytes in gaseous or liquid samples by simultaneous or quasi-simultaneous determination of characteristic spectral absorption lines of atoms, ions or molecules and the corresponding background absorption, which is caused by interfering substances in the sample.
  • the invention relates to the corresponding photometric determination of mercury in gaseous samples.
  • Harmful heavy metals especially mercury.
  • mercury In addition to mercury are in the flue gases also usually other typical ingredients such as SO2, SO3, HX, X2 (where X is a halogen) included.
  • SO2, SO3, HX, X2 where X is a halogen
  • limit values are prescribed by law, which must not be exceeded. For this reason, in such emissions releasing plants, such as e.g.
  • the pollutant to be measured often has to be present in a form suitable for detection and possibly converted therefor.
  • the pollutant to be measured often has to be present in a form suitable for detection and possibly converted therefor.
  • mercury which is present in flue gases, usually as a mercury compound, this is converted into elemental mercury.
  • CONFIRMATION COPY It would therefore be advantageous to be able to provide a detector system with which it is easier and faster than previously to detect pollutants from gaseous or liquid emissions qualitatively and quantitatively in a position.
  • Atomic absorption spectra are narrow band, i. Atoms absorb light of a defined wavelength, while the absorption spectra of molecules absorb over a more or less large wavelength range, ie are broadband.
  • Elemental mercury for example, has an intense but very narrow band absorption line at 253.6 nm to 253.7 nm. This issue is used in the prior art for the qualitative and quantitative analysis of mercury, for example by means of AAS. There, the attenuation of a monochromatic light beam of exactly this wavelength is determined. However, this known method works only after complete removal of all 253.6 nm also absorbing impurities or impurities from the sample to be measured or from the beam path, usually after consuming and time consuming matrix removal.
  • the method according to the invention comprises a mercury measurement almost simultaneously with the measurement of the measurement of the alternative (competitor) absorber or interfering substances necessary for correction directly from the sample within a single and low-resolution spectrometer system.
  • the invention thus provides a method for the simultaneous photometric qualitative and quantitative determination of an analyte of atoms, ions or molecules, preferably mercury, in a sample, which additionally
  • spectrometric arrangement a photometric measurement signal of the sample in the narrow-band spectral absorption range of the analyte to be determined and a photometric measurement signal of the sample in the broadband spectral
  • Absorption area for detecting the interfering substances are generated, these measurement signals are evaluated, and from which the analyte is determined qualitatively and quantitatively by means of known analysis.
  • a narrowband, preferably monochromatic light source and simultaneously or in parallel a broadband light sources are used.
  • the narrowband or monochromatic light source is selected with respect to its wavelength to be absorbed to correspond to the wavelength at which the emission substance to be measured, for example mercury, absorbs.
  • the emission substance to be measured for example mercury
  • the broadband wavelength depends essentially on the substances which likewise absorb in this region and which superimpose the monochromatic absorption spectral line. In most cases, this is a light source, the light in a wavelength range of the near UV, ie between 200 nm and 400 nm. Of course, light sources are also suitable here, covering even a wider spectrum in the invisible and visible range.
  • the subject of the invention is a corresponding process in which the narrowband and broadband light sources and the spectrometer are adapted to measure different analytes.
  • the metals often occur in the exhaust gases / flue gases also in bound form. It is possible to reduce mercury by adding CO or other reducing agents to the flue gas, such as copper, to the element. Other metal compounds can be reduced in a similar manner. Mercury from compounds can also be converted to an element by amalgamation.
  • the invention also works with (broad or narrow band) compounds, both of mercury and compounds of other elements.
  • metal compounds such as
  • the method according to the invention is carried out using an absorption spectrometer
  • the invention thus relates to a corresponding method in which the sample is irradiated with the analyte to be determined, preferably mercury, and the interfering substances present in the wavy line of the absorber in a flow cell in succession or alternately with the narrowband and the broadband light source and the absorption spectra are measured ,
  • Disturbing substances that are at the said wavelength of mercury are mainly SO2, SO3 or halogen compounds in question, which the Cover or overlay absorption line of mercury, which can be concluded from a single measurement with monochromatic light alone, not on the existence and especially on the quantity of mercury.
  • the chemometry can be used if necessary.
  • the invention is furthermore also a simultaneous spectrometer for the simultaneous qualitative and quantitative determination of atoms, molecules and ions, preferably mercury, said 's spectrometer comprises at least the following items:
  • a narrow band, preferably monochromatic light source having a wavelength which is absorbed by the analyte to be determined - in the case of mercury at 253.6 or 253.7 nm - and
  • Hollow cathode lamps, laser diodes, gas radiators or multicolored light sources are suitable as light sources for the simultaneous spectrometer according to the invention.
  • the incident light and optionally the incident light of the said light sources is controlled according to the invention by shutter and / or trigger, which is advantageous for the synchronization of the measurements.
  • the liquid or gaseous, preferably gaseous, samples to be measured are analyzed with the aid of correspondingly dimensioned (according to the required intensities to be measured) cuvettes, preferably flow cuvettes, in particular multi-OPL cuvettes.
  • the simultaneous spectrometer according to the invention can also have a plurality of different light sources simultaneously with different cuvette channels and / or additional reference channels.
  • a diode detector is used in which each diode represents a different narrow wavelength range.
  • Figure 1 describes the schematic structure of the spectrometer according to the invention:
  • the spectrometer is constructed as shown schematically in Figure 1. It has two light sources, which emits a light source (2) light of a certain wavelength, here the wavelength of mercury (253.6 nm).
  • a gas cell is alternately irradiated by the broadband light source (1) and the line emitter (2) (in this case in resonance with mercury).
  • the spectral light intensity is measured behind the cuvette (6) by means of a spectrometer (7).
  • the spectrometer is alternately different, each optimally controlled for the irradiation of one or the other light source.
  • the one case then gives the absorption of the mercury line and the other the measure of the absorption of molecules competing there, the so-called background. In this way, virtually the same time the measurement signal and the possibly necessary
  • the concentrations of the mercury measurement interfering molecules can also be determined in addition.
  • the evaluation of a measurement is explained using the example of mercury determination:
  • the measurement using the narrow-band light source provides the value of the light absorption at 253.6 nanometers. This absorption is additively composed of the contribution of mercury itself and the contributions of all other species which absorb at this wavelength, including broadband.
  • the measurement using the broadband light source provides the value of light absorption at 253.6 nanometers and the spectral environment around that wavelength.
  • Equation 2 With the intensity ratio determined from Equation 4, the unknown factor in Equation 2 is determined and CH 9 can be calculated.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

L'invention concerne un procédé et un appareil de mesure pour la détermination qualitative et quantitative de substances à analyser dans des échantillons gazeux ou liquides par détermination simultanée ou quasi-simultanée de lignes d'absorption spectrale caractéristiques d'atomes, d'ions ou de molécules et de l'absorption de fond correspondante provoquée par des substances interférentes dans l'échantillon. L'invention concerne en particulier la détermination photométrique correspondante de mercure dans des échantillons gazeux.
PCT/EP2012/001167 2011-03-16 2012-03-15 Procédé et appareil de mesure pour la détermination d'atomes et de molécules dans des échantillons d'analyse WO2012123124A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12715817.8A EP2686666A1 (fr) 2011-03-16 2012-03-15 Procédé et appareil de mesure pour la détermination d'atomes et de molécules dans des échantillons d'analyse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE202011004065U DE202011004065U1 (de) 2011-03-16 2011-03-16 Online- Simultanmessgerät für Atome und Moleküle
DE202011004065.8 2011-03-16

Publications (1)

Publication Number Publication Date
WO2012123124A1 true WO2012123124A1 (fr) 2012-09-20

Family

ID=45557580

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/001167 WO2012123124A1 (fr) 2011-03-16 2012-03-15 Procédé et appareil de mesure pour la détermination d'atomes et de molécules dans des échantillons d'analyse

Country Status (3)

Country Link
EP (1) EP2686666A1 (fr)
DE (1) DE202011004065U1 (fr)
WO (1) WO2012123124A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020160922A1 (fr) * 2019-02-07 2020-08-13 Analytik Jena Ag Spectromètre d'absorption atomique
WO2021239536A1 (fr) * 2020-05-28 2021-12-02 Ams International Ag Spectromètre d'absorption optique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108956508A (zh) * 2018-09-20 2018-12-07 上海安杰环保科技股份有限公司 一种断续流动进样的气相分子吸收光谱仪及检测方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3571589A (en) * 1969-06-04 1971-03-23 Barringer Research Ltd Method for absorption analysis using a source having a broadened emission line
US3825344A (en) * 1971-09-14 1974-07-23 Commissariat Energie Atomique Device for analysing a substance by atomic absorption with background correction
US5042946A (en) * 1990-05-02 1991-08-27 Hitachi, Ltd. Atomic absorption spectrophotometric method and apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3571589A (en) * 1969-06-04 1971-03-23 Barringer Research Ltd Method for absorption analysis using a source having a broadened emission line
US3825344A (en) * 1971-09-14 1974-07-23 Commissariat Energie Atomique Device for analysing a substance by atomic absorption with background correction
US5042946A (en) * 1990-05-02 1991-08-27 Hitachi, Ltd. Atomic absorption spectrophotometric method and apparatus

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020160922A1 (fr) * 2019-02-07 2020-08-13 Analytik Jena Ag Spectromètre d'absorption atomique
CN113383217A (zh) * 2019-02-07 2021-09-10 耶拿分析仪器有限公司 原子吸收光谱仪
WO2021239536A1 (fr) * 2020-05-28 2021-12-02 Ams International Ag Spectromètre d'absorption optique

Also Published As

Publication number Publication date
EP2686666A1 (fr) 2014-01-22
DE202011004065U1 (de) 2012-01-02

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