EP1851530A2 - Procede et dispositif pour determiner la concentration en halogenes lies organiquement - Google Patents

Procede et dispositif pour determiner la concentration en halogenes lies organiquement

Info

Publication number
EP1851530A2
EP1851530A2 EP06707256A EP06707256A EP1851530A2 EP 1851530 A2 EP1851530 A2 EP 1851530A2 EP 06707256 A EP06707256 A EP 06707256A EP 06707256 A EP06707256 A EP 06707256A EP 1851530 A2 EP1851530 A2 EP 1851530A2
Authority
EP
European Patent Office
Prior art keywords
measuring device
concentration
sample
organically bound
halogens
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06707256A
Other languages
German (de)
English (en)
Inventor
Christian Buck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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
Priority claimed from DE200520006570 external-priority patent/DE202005006570U1/de
Priority claimed from DE202005010595U external-priority patent/DE202005010595U1/de
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1851530A2 publication Critical patent/EP1851530A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1826—Organic contamination in water
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/19—Halogen containing
    • Y10T436/193333—In aqueous solution

Definitions

  • the invention relates to a method for determining the concentration of organically bound halogens or the like present in flow systems such as waste water.
  • the invention will be described below using the example of determining the concentration of organically bound halogens.
  • concentration determination described can be in the same way directly on the determination of the concentration of other substances in the
  • wastewater such as the concentrations of AOX, EOX, BTEX, alcohols, peroxides, metals, aldehydes, ketones, polymers, aromatics, functionalized aromatics or polyaromatics.
  • AOX is a sum parameter for adsorbable organically bound halogens, the size of which should give a statement about the toxicity of wastewater. Typical AOX concentrations in wastewater are zero to a few ppm, and regulatory limits are typically around one ppm.
  • EOX is a sum parameter for elutable organically bound halogens, the size of which also makes it possible to make a statement about wastewater.
  • BTEX is the parameter for the sum of benzene, toluene, ethylbenzene and xylene.
  • the essential components of a conventional sewage treatment plant such as primary sedimentation tanks, balancing tanks, bioreactors, secondary settling tanks, etc. represent a very large volume.
  • a plant with 100,000 population equivalents is filled with some 10,000 m3 of water in operation, typical inflow and outflow amounts are some 100 m3 each Hour.
  • Such a plant is normally operated continuously and has the task of eliminating nutrients and pollutants from the feed water.
  • a portion of the stream to be investigated is continuously branched off over a large period of time and combined to form a continuous mixed sample (for example a 24-h mixed sample).
  • the continuous mixing sample is homogenised after the sampling time and an aliquot of it is examined in the laboratory with a judicious method (DIN EN 1485 (H 14) or DIN 38409 (H 22)) for traces of harmful substances.
  • the time required to perform an AOX measurement in accordance with DIN adds up to about 1.5 hours per sample to be examined without sample logistics.
  • an aliquot of a water sample is usually spiked with a fixed amount of activated carbon and stirred for one hour.
  • the filter cake is freed from inorganic halides by washing with dilute HNO3 and dried slightly.
  • the purified filter cake is completely oxidized in a combustor in the oxygen stream.
  • the adsorbed organically bound halogens are completely mineralized and together with all others
  • Oxidation products transferred to a water-filled storage vessel The now inorganic halides go there in solution and can be determined electrochemically in their concentrations. This method is tedious and therefore expensive.
  • the object of the invention is therefore to design a measuring method such that a rapid and automatable determination of the concentration of AOX and the like is possible.
  • This invention is achieved by a method for determining the concentration of organic halogens in wastewater, whereby a predetermined amount of waste water is taken and transferred to a measurement sample, a spectral measurement is performed on the measurement sample and the result of the spectral measurement with reference measurements is compared to determine the concentration of organically bound halogens.
  • a precise and lengthy measurement of the concentration of organically bound halogens by means of a complex separation of the organically bound halogens and their concentration measurement by electrochemical methods is determined by spectral measurements at least approximately applicable characteristic for the concentration to be determined. It comes in advance Reference measurements to be carried out are of great importance, since the various AOX contributors may comprise several substance classes and the characteristic spectral properties of the individual substances may be very different.
  • the location, shape and intensity of characteristic emission or absorption lines vary depending on additional molecular groups or environmental conditions.
  • a new spectral measurement with an unknown concentration of AOX contributors can be carried out very quickly and precisely evaluated, or the unknown concentration can be determined.
  • the spectral measurements and their evaluation can be carried out quickly and automatically. It has been found that the time required for such a measurement, including the required sampling and preparation of the sample is about 15 minutes or less, so that a quasi-continuous detection of the particularly relevant pollutant concentrations is possible.
  • the organically bound halogens be enriched in the measurement sample before the spectral measurement is performed.
  • Such enrichment can be achieved by enriching the organically bound halogens by extraction with a suitable extractant.
  • Another, likewise advantageous possibility for improving the detection sensitivity consists of influencing their optical properties by suitable derivatization of the organically bound halogens.
  • suitable derivatization of the organically bound halogens By rapidly and easily practicable derivatization of those substances which contribute to the concentration to be measured, their optical activity could be increased and thus the detection sensitivity of the spectrometer for these substances improved.
  • the reliability and accuracy of the measurement method can be further increased by removing inorganic halogens from the measurement sample.
  • chemometric methods are used to compare the spectral measurement with reference measurements to those contained in the wastewater
  • Chemotnetrie is a mathematical-statistical method for the extraction of physical or chemical information from single- and multi-dimensional data sets.
  • the reproduction of the spectrum of a pure substance A from a set of A containing mixture spectra is possible if in a chemometric method on the basis of calibration spectra (spectra of A in known concentration containing mixtures) a relationship was determined.
  • calibration spectra spectra of A in known concentration containing mixtures
  • predictive models for the concentration of A in A containing mixtures can be generated.
  • Chemometric methods are particularly suitable for the generation of predictive models of AOX contributors, or similar sum parameters, since the optical properties of the many different substances that contribute to the concentration to be determined, depending on environmental conditions such as the temperature, the pH, salinity or, more generally, matrix effects.
  • the effort required for generating and evaluating reference measurements can be significantly reduced by using chemometric methods, without the result of a corresponding deterioration in the concentration determination.
  • this method is applicable to the determination of the concentration of substance groups and to the determination of physicochemical and colligative properties of mixtures of substances.
  • a number of mathematical procedures are known on the subject, such as regularized discriminant analysis (RDA), principal component analysis (PCR), least-squares (PLS) or multiple linear regression (MLR).
  • chemometrics is not restricted to spectroscopic data, but spectroscopic data are useful when it comes to
  • Characterization of material or system properties are particularly easy and fast to generate.
  • an optical spectral measurement is performed on the measurement sample in the liquid state.
  • the optical spectral measurement preferably includes a measurement of the fluorescence spectrum.
  • other optical properties of the test sample such as
  • the sensitivity of the optical spectrometers used for this purpose may be in the optical wavelength range, but may additionally or instead comprise the infrared range or the ultra-violet wavelength range.
  • the Measuring sample is a solid phase extract with organically bound halogens is removed and on the solid phase extract, an optical spectral measurement is performed.
  • the optical spectral measurement may then conveniently include a measurement of the reflection spectrum or the fluorescence spectrum.
  • Natural frequency is introduced into the measurement sample, wherein the oscillatory device consists of a material to which preferably attaches organically bound halogens, and that removed after a predetermined time, the oscillatory device and the change of the natural frequency is determined.
  • Suitable oscillatory devices may be, for example, electromagnetic resonant circuits or vibrating masses such as quartz crystals or the like.
  • the natural frequency of a device capable of oscillating may depend, inter alia, on the geometry or the mass assignment of an oscillatable structure. Its natural frequency changes in particular when the surface or the inert mass is changed by substance coverage.
  • the peculiarity of the proposed method is based on constructing the oscillatory device from a material which has a particular affinity for the substances to be determined (analytes), which are suitable as an indicator of the pollutants to be determined.
  • analytes substances to be determined
  • the amount of substance of the deposited analyte causes a change proportional to this amount of the natural frequency of the oscillatory device.
  • the natural frequency of the oscillatory device can now be determined before and after its exposure in the test sample to be examined.
  • the resonance amplitude is proportional to the fourth power of the difference between the natural vibration frequencies of the oscillatory device and the external resonant circuit, the resonance amplitude provides a signal which is very sensitive to changes in the analyte occupancy on the oscillatory device and thus to the analyte concentrations in the measurement sample.
  • the invention also relates to an automatic measuring device.
  • the known methods require a plurality of method steps, which at a reasonable cost so far can only be processed manually and are therefore carried out only at intervals of days or the like.
  • An automation of the known methods would be due to the different devices and devices associated with a very significant cost, which in an unfavorable
  • An automatic measuring device for the automatic measurement of organically bound halogens has a device for taking a sample amount from a flow system, a device for transferring the Sample quantity in a measurement sample, a device for performing spectral measurements on the measurement sample and an evaluation device for evaluating the result of the spectral measurements with reference measurements on to determine the concentration of organic halogens.
  • the measuring device may have a device for accumulating organically bound halogens in the test sample.
  • the device for enriching is an extraction device.
  • the measuring device is a device for
  • Derivatizing of organically bound halogens in the sample has. By suitable derivatization of the substances to be detected, their optical activity can be stimulated or increased.
  • the measuring device will include a device for removing inorganic halogens from the sample.
  • the evaluation device has a memory unit for reference measurements and an evaluation unit for the comparison of the spectral measurement with reference measurements by means of chemometric methods in order to determine the concentration of organically bound halides contained in the wastewater.
  • the device for carrying out a spectral measurement has an optical spectrometer.
  • the optical spectrometer has, for example
  • the spectrometer has a device for measuring an X-ray fluorescence spectrum, a reflection spectrum, an emission spectrum or a transmission spectrum.
  • the optical spectrometer is adapted to perform measurements on liquid samples.
  • Measuring device comprises a device for transferring the sample into a solid phase extract with organically bound halogens and that the optical spectrometer comprises a device for measuring a reflection spectrum.
  • concentration of, for example adsorbable on activated carbon organically bound halogens can be determined quickly and automatable and thus cost, without a subsequent conversion would be required.
  • adsorption apparatus for automatically increasing the concentration to be determined, a predetermined volume of the sample is passed through an activated carbon compact, or mixed with activated charcoal, stirred and filtered off. The adsorbed on the activated carbon amount of substance is freed by washing of inorganic halide.
  • the concentration of organically bound halogens can be increased by several orders of magnitude and thereby subsequent measurements can be improved in their accuracy.
  • the measuring device has a vibratory device with a known natural frequency, which can be introduced into the test sample for a predetermined duration, wherein the oscillatory device consists of a material to which preferably bound organic halogens , And that with the apparatus for performing spectral measurements, a change in the natural frequency of the oscillatory device is measurable.
  • the measuring device has a conversion unit, by means of which at least an optionally required conversion of the determined concentration of organically bound halogens into a concentration of adsorbable organically bound halogens can take place.
  • the measuring device comprises a device for the automatic provision of a sample quantity from a laboratory or from having a flow system. It is likewise provided that the measuring device has a device for the automatic transfer of the test sample into the device for carrying out the spectral measurement.
  • the measuring device has a signaling device with which a transmissible signal can be generated. In this way, depending on the measured pollutant concentration control of the treatment plant and. in particular a rapid diversion of the inlet into a separate basin.
  • Concentration of other spectroscopically active substances in particular the concentrations of AOX contributors, BTEX contributors, alcohols, peroxides, metals, aldehydes, ketones, polymers, aromatics, functionalized aromatics or polyaromatics.
  • the described concentration determination can be carried out substantially unchanged on a gaseous measurement sample as well.
  • FIG. 1 shows a schematic process flow for measuring an AOX concentration in waste water
  • FIG. 2 shows a schematic illustration of a measuring device used for carrying out the method illustrated in FIG. 1.
  • a chemometric calibration model for the AOX concentration in wastewater is created.
  • further calibration models for example for the BTEX concentration in waste water, or the concentrations in suitable extracts of AOX or BTEX-containing wastewater can be prepared.
  • a predetermined amount of wastewater is removed in a first process step 2 and transferred into a measurement sample.
  • a spectral measurement is carried out on the test sample in a further method step 3.
  • the result of the spectral measurement is compared in a method step 4 with reference measurements or with the calibration models in order to determine the concentration of the organically bound halogens.
  • the concentration of the pollutants to be measured In order to improve the detection sensitivity, the concentration of the pollutants to be measured, or
  • Pollutant indicators are enriched.
  • the test sample with an unknown concentration of AOX or BTEX is extracted in an additional method step 5 after the sampling and before the measurement.
  • these reference measurements must be extracted in the same way have been.
  • a spectrum is then measured in method step 3 already described, which can be evaluated by comparison with the corresponding calibration models.
  • the method proposed here works in such a way that an optical spectrum of an organic extract of the sample to be examined in method step 4 is evaluated according to a chemometric calibration model.
  • the ultraviolet, the visual or the infrared spectral range or a combination thereof should be used for this purpose. It is also conceivable to extend the spectral measurements to X-rays or high-energy radiation.
  • Aromatics according to BTEX have a substantial optical activity in the ultraviolet-visual spectral range (UV-Vis), or in fluorescence. Their usually strong dilution in the sewage often makes a direct measurement difficult. In particular, a dilution of the spectrally active and sought substance represents a weakening of the evaluable signal and leads to an unfavorable signal-to-noise ratio during the measurements.
  • UV-Vis ultraviolet-visual spectral range
  • the detection limit of chlorobenzene in water is about 10-5. If chlorobenzene is the only AOX feed with a concentration of a few ppm, then it is the sensitivity of UV-Vis spectroscopy in transmission at least 1 order too low.
  • Enrichment can be carried out easily and quickly with today's commercially available process machines.
  • a last method step 7 the measuring device used is cleaned and in particular freed of organically bound halogens.
  • a subsequent measurement can be started immediately with the method step 2 already described above.
  • An automated measuring device 9 for the automatic measurement of organically bound halogens shown only by way of example in FIG. 2, has one
  • Extraction device 10 for a given amount of sample from a flow system with wastewater on.
  • a transfer device 11 By means of a transfer device 11, the amount of sample is transferred into a reusable measurement sample.
  • the measurement sample is with the transfer device 11 immediately one
  • the optical spectrometer 12 has a device, not shown, for measuring a
  • Transmitted light spectrum for example a measuring cuvette.
  • the spectrometer 12 is connected to an evaluation device 13 for evaluating the result of the spectral measurements with reference measurements.
  • the evaluation device 13 has a memory unit 14 for already performed reference measurements and an evaluation unit 15 for the comparison of the spectral measurement with stored reference measurements by means of chemometric methods in order to determine the concentration of organically bound halides contained in the wastewater.
  • the measuring device 9 has a device for enriching 16 of organically bound halogens in the test sample.
  • the enrichment device 16 is an extraction device, which is expediently integrated into the transfer device 11.
  • the solvent used for the extraction is a halogen-free solvent.
  • the transfer device may also comprise a device 17 for reducing or eliminating inorganic halogens.
  • the devices and apparatus described as individual devices 10 and 11 or 13 to 17 can each be configured as a unit of a single, suitably adapted laboratory robot.
  • the devices 10 to 12, or 16 and 17, which come into contact with the test sample either each have separate cleaning devices, not shown, or can each have a respective associated or common not shown
  • Cleaning device are supplied to be cleaned after the removal and measurement of a sample and prepared for a new measurement.
  • the measuring device has a signaling device 18 with which a transferable signal can be generated.
  • the signaling device 18 is connected by means of signal lines 19 with control devices, not shown, of the sewage treatment plant, also not shown.

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  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • Immunology (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

L'invention concerne un procédé pour déterminer la concentration en halogènes liés organiquement dans des eaux usées. Ce procédé consiste : à prélever une quantité prédéfinie d'eaux usées, et à transférer cette quantité vers un échantillon d'essai ; à soumettre cet échantillon d'essai à une mesure spectrale, et à comparer le résultat de la mesure spectrale avec des mesures de référence, pour déterminer la concentration en halogènes liés organiquement. Les halogènes liés organiquement sont concentrés dans l'échantillon d'essai, par extraction ou adsorption, et sont retirés de l'échantillon d'essai. La comparaison entre la mesure spectrale et des mesures de référence est effectuée à l'aide de procédés chimiométriques. Cette invention concerne également un dispositif de mesure automatique (9) comprenant : un dispositif (10) servant à prélever une quantité d'échantillon dans un système à écoulement ; un dispositif (11) conçu pour transférer la quantité d'échantillon vers un échantillon d'essai ; un dispositif (12) servant à effectuer des mesures spectrales sur l'échantillon d'essai, et ; un dispositif d'évaluation (13) qui est destiné à évaluer le résultat des mesures spectrales au moyen de mesures de référence. Le dispositif de mesure selon l'invention comprend également un dispositif pour préparer automatiquement une quantité d'échantillon, et un dispositif (11) pour transférer automatiquement l'échantillon d'essai vers le dispositif (12) servant à effectuer les mesures spectrales. Ledit dispositif de mesure peut également être utilisé pour déterminer la concentration d'autres substances spectroscopiquement actives, à savoir la concentration de contributeurs AOX, de contributeurs BTEX, d'alcools, de peroxydes, de métaux, d'aldéhydes, de cétones, de polymères, d'aromates, d'aromates fonctionnalisés, ou de polyaromates.
EP06707256A 2005-02-25 2006-02-24 Procede et dispositif pour determiner la concentration en halogenes lies organiquement Withdrawn EP1851530A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE202005003171 2005-02-25
DE200520006570 DE202005006570U1 (de) 2005-04-23 2005-04-23 Vorrichtung zur schnellen Onlinemessung von AOX und BTEX mittels Extraktion, Spektroskopie und Chemometrie
DE202005010595U DE202005010595U1 (de) 2005-02-25 2005-07-04 Vorrichtung zur schnellen Onlinemessung von AOX sowie von Quecksilber und Chalkogenen
DE202005010988 2005-07-12
PCT/EP2006/001717 WO2006089773A2 (fr) 2005-02-25 2006-02-24 Procede et dispositif pour determiner la concentration en halogenes lies organiquement

Publications (1)

Publication Number Publication Date
EP1851530A2 true EP1851530A2 (fr) 2007-11-07

Family

ID=36228793

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06707256A Withdrawn EP1851530A2 (fr) 2005-02-25 2006-02-24 Procede et dispositif pour determiner la concentration en halogenes lies organiquement

Country Status (5)

Country Link
US (1) US20080153173A1 (fr)
EP (1) EP1851530A2 (fr)
JP (1) JP2008532023A (fr)
AU (1) AU2006218103A1 (fr)
WO (1) WO2006089773A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5764799B2 (ja) * 2011-03-29 2015-08-19 国立研究開発法人産業技術総合研究所 フッ素化不飽和炭化水素の検出方法及び検出センサー
JP5830796B2 (ja) * 2011-03-29 2015-12-09 国立研究開発法人産業技術総合研究所 フッ素化炭化水素化合物の検出方法及び検出センサー
JP5764798B2 (ja) * 2011-03-29 2015-08-19 国立研究開発法人産業技術総合研究所 フッ素化炭化水素の検出方法及び検出センサー
CN111982952A (zh) * 2020-09-03 2020-11-24 北京赛诺新炜科技有限公司 一种有机卤化物检测装置及使用方法

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US5028543A (en) * 1988-03-18 1991-07-02 Dexsil Corporation Method for measuring the content of halogenated organic compounds in soil samples
US5222032A (en) * 1990-10-26 1993-06-22 E. I. Du Pont De Nemours And Company System and method for monitoring the concentration of volatile material dissolved in a liquid
AU5522594A (en) * 1993-03-03 1994-09-08 W.R. Grace & Co.-Conn. A method of directly monitoring the concentrations of microbiocides in aqueous systems
US5364797A (en) * 1993-05-20 1994-11-15 Mobil Oil Corp. Sensor device containing mesoporous crystalline material
US5358875A (en) * 1993-06-25 1994-10-25 Fic - Fiberchem, Inc. Method and composition for halohydrocarbon detection
US5445008A (en) * 1994-03-24 1995-08-29 Martin Marietta Energy Systems, Inc. Microbar sensor
US5691205A (en) * 1994-06-23 1997-11-25 Canon Kabushiki Kaisha Fluorometric analysis of chloride ion and chemical sensor therefor
US5547877A (en) * 1994-10-25 1996-08-20 Ensys Environmental Products, Inc. Methods for the rapid detection of toxic halogenated hydrocarbons and kits useful in performing the same
DE10138428B4 (de) * 2001-08-06 2004-07-22 Ech Elektrochemie Halle Gmbh Verfahren zur summarischen Bestimmung von Organochlor-, Organobrom-, Organoiod- und/oder Organoschwefelverbindungen

Non-Patent Citations (1)

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Title
See references of WO2006089773A2 *

Also Published As

Publication number Publication date
WO2006089773A2 (fr) 2006-08-31
US20080153173A1 (en) 2008-06-26
AU2006218103A1 (en) 2006-08-31
JP2008532023A (ja) 2008-08-14
WO2006089773A3 (fr) 2007-04-26

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