EP2609388B1 - Four haute température, utilisation d'une céramique de type spinelle et procédé permettant d'effectuer des mesures du c(o)t dans des échantillons - Google Patents

Four haute température, utilisation d'une céramique de type spinelle et procédé permettant d'effectuer des mesures du c(o)t dans des échantillons Download PDF

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Publication number
EP2609388B1
EP2609388B1 EP11748415.4A EP11748415A EP2609388B1 EP 2609388 B1 EP2609388 B1 EP 2609388B1 EP 11748415 A EP11748415 A EP 11748415A EP 2609388 B1 EP2609388 B1 EP 2609388B1
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EP
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Prior art keywords
temperature furnace
sample
vaporization space
spinel ceramic
ceramic
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EP11748415.4A
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German (de)
English (en)
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EP2609388A1 (fr
Inventor
Christian Heuckeroth
Rudolf Kreutzer
Peter Kawulycz
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Priority to EP11748415.4A priority Critical patent/EP2609388B1/fr
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B17/00—Furnaces of a kind not covered by any preceding group
    • F27B17/02—Furnaces of a kind not covered by any preceding group specially designed for laboratory use

Definitions

  • the present invention relates to a high-temperature furnace, with the aid of which T (O) C measurements of samples can be carried out in order to be able to determine, in particular according to DIN EN 1484, the fraction of oxidizable carbon of a wastewater.
  • the present invention further relates to a suitable use of a spinel ceramic and a method for carrying out T (O) C measurements of samples.
  • the proportion of oxidizable carbon of a wastewater is determined by determining the TOC value (English: total organic carbon), whereby the measured carbon content does not necessarily have to be organically bound depending on the sample ( "T (O) C-value").
  • TOC value English: total organic carbon
  • T (O) C-value the concentration of the resulting CO 2 can be determined over time using an NDIR (Non-Dispersive Infrared Detector). The resulting integral of the CO 2 concentration over time is proportional to the carbon released from the sample.
  • the high-temperature reactor is heated to temperatures of about 700 ° C to 1000 ° C.
  • T (O) C measurement it has been found that after some time salts deposit, which impairs the T (O) C measurement, so that the high-temperature furnace aged by the salt deposits has to be slowly cooled and manually cleaned at certain maintenance intervals before the high-temperature reactor is again slow can be heated to the operating temperature.
  • the high-temperature furnace according to the invention for T (O) C measurement of a sample has a furnace housing delimiting a evaporation chamber, which has a sample opening for dripping in the sample.
  • the furnace housing is lined with a spinel ceramic on an inner side facing the evaporation space.
  • the evaporation space is the entire volume, which is limited by the oven housing.
  • the evaporation space is lined by a material that allows particularly high temperatures within the evaporation space and thus the most complete combustion and at the same time is very resistant to thermal shock.
  • This makes it possible to substantially clean the evaporation space at operating temperature with a rinsing liquid and dissolved salts, in particular recrystallized inorganic salts from the evaporation space dissolved in the rinsing liquid or to remove undissolved. Aging of the high-temperature furnace by deposited salts can thereby be avoided or at least significantly delayed, whereby the operating costs over the life of the high-temperature furnace are reduced. Cleaning by hand is not required.
  • a cleaning of the remaining at operating temperature high temperature furnace between two measurements can be provided without the particular continuous T (O) C measurement of samples is significantly delayed.
  • Damage to the spinel ceramic by the impinging rinse liquid can be avoided due to the high thermal shock resistance, so that microcracks and material fatigue of the spinel ceramic during rinsing are substantially avoided.
  • increased corrosion resistance, especially in the case of alkali-containing slags, is achieved, so that the range of application of the high-temperature furnace can be extended to a large number of different, for example particularly alkaline, samples.
  • the spinel ceramic does not react acid with water, whereas, for example, an Al 2 O 3 -SiO 2 ceramic reacts acidically with water as a conventional ceramic.
  • the occurrence of additional acid can be avoided, which relieves in particular the analysis.
  • the measurement accuracy can be improved because subsequent measurements are not affected by deposited salts.
  • This allows fast and accurate online T (O) C measurement, in particular of wastewater, such as those that occur during the operation of chemical plants.
  • the properties of spinel ceramics can be adapted by using different powders with different additives during production.
  • different particle sizes and / or particle size distributions can be set for the spinel ceramic.
  • different activated and / or non-activated phases can be provided in each case with corresponding components provided.
  • a spinel ceramic is understood in particular to mean a ceramic material which has the structure of a spinel.
  • a ceramic is a material which has been sintered in particular by annealing or firing fine-grained, inorganic material at elevated temperatures, for example in a range of ⁇ 900 ° C to ⁇ 1500 ° C. Ceramics often have preferred properties with respect to temperature resistance, hardness, electrical insulation, chemical resistance, et cetera.
  • a spinel structure is a cubic structure which can be formed by a compound of the general type AB 2 X 4 , where A and B are in particular metallic elements. In this case, A may be a divalent metal cation, B may be a trivalent metal cation and X may be an oxide.
  • divalent cations examples include Mg 2+ , Fe 2+ , Zn 2+ , Mn 2+ , Cu 2+ , Ne + , Co 2+
  • trivalent cations may in particular be formed by Al 3+ , Fe 3+ , Mn 3+ , Cr 3+ , Fe 3+ , Ga 3+ .
  • Special spinels which may be suitable according to the invention include in particular the usual spinel (MgAl 2 O 4 ), zinc spinel (ZnAl 2 O 4 ), iron spinel (Fe, Mg) (Al, Fe) O 4 , chromium spinel (Fe, Mg) ( Al, Cr, Fe) 2 O 4 or nickel spinel (NiAl 2 O 4 ).
  • the spinel ceramic according to the invention comprises materials as described above, as well as materials which have mixed mixed crystals as substitution mixed crystals, as well as crystals with defect sites.
  • the composition can vary within wide limits.
  • stoichiometric MgAl 2 O 4 spinels are also included in the invention, such as MgO-rich and Al 2 O 3 -rich spinels, respectively.
  • the furnace housing has at least one flushing opening for introducing a flushing liquid.
  • the flushing opening may in particular be different from the sample opening, so that the flushing liquid does not contaminate the path of the sample and may possibly falsify a subsequent measurement.
  • the flushing opening is oriented substantially vertically, so that the flushing liquid can trickle down in the direction of gravity over the surface of the spinel ceramic facing the evaporation space in order to clean the high-temperature furnace.
  • the at least one flushing opening is preferably aligned substantially horizontally, so that the flushing liquid can run along the boundary of the evaporation space via the side of the spinel ceramic facing the evaporation chamber.
  • the rinsing liquid can be discharged together with the washed out salts, which may be dissolved in the rinsing liquid or undissolved, in particular via a lower outlet in the direction of gravity.
  • Rinsing liquid remaining in the evaporation space can be vaporized and discharged from the evaporation space, comparable to a sample measurement.
  • rinsing liquid water can be used.
  • an organic, in particular carbonaceous, solvent as rinsing liquid. By anyway provided CO 2 measurement can be determined when the rinse liquid is completely evaporated and removed from the vaporizing space.
  • the flushing opening is preferably connected to at least one injection nozzle for introducing an aerosol mist from flushing liquid, wherein the at least one injection nozzle has a substantially horizontally oriented introduction direction.
  • the rinsing liquid can thereby be introduced as mist or vapor and sprayed at a corresponding pressure against the respective rinsing opening opposite region of the spinel ceramic.
  • the rinsing liquid can more easily detach from the baked salts by the impact pressure which can be achieved thereby on the spinel ceramic.
  • a multiplicity of flushing openings is preferably uniformly distributed in the circumferential direction at a substantially common vertical height.
  • the spinel ceramic comprises at least one additive which is selected from liquefiers, ceramic fibers or further inorganic fillers. It is particularly preferred if at least one additive in the ceramic is finely dispersed or distributed. In this way, an adaptation to special requirements of the spinel ceramic can be realized.
  • a condenser also known as water reducer, superplasticizer or dispersant
  • water reducer also known as water reducer, superplasticizer or dispersant
  • dispersant significantly reduces the need for mixing water. Due to the dispersion, all grains can be wetted homogeneously from all sides despite a lower water content.
  • the ceramic can be optimized, for example, with respect to thermal shock resistance or surface finish and adapted to the desired requirements.
  • the spinel ceramic has a discontinuous particle size distribution.
  • the thermal shock resistance or the thermal shock behavior is further improved.
  • the thermal shock resistance is particularly important for flushing the furnace.
  • a discontinuous particle size distribution in the context of the invention means that the particle size distribution has a gap in a certain particle size range.
  • the spinel ceramic may have 60-65 mass% coarse grain and 35-40 mass% fine grain, the fine grain may comprise grain sizes in a range of ⁇ 1 ⁇ m to ⁇ 74 ⁇ m and the coarse grain grain sizes in a range of ⁇ 74 ⁇ m to ⁇ 700 ⁇ m ( ⁇ means greater than or equal to, ⁇ means less than or equal to).
  • the spinel ceramic has pores having a size in a range of ⁇ 10 ⁇ m.
  • Such small pores further improve the thermal shock resistance and, if crack formation nevertheless occurs, result in a rounding of the crack tip, which leads to lower stress at the corresponding point.
  • the pores may in particular have a size of ⁇ 0.1 ⁇ m to ⁇ 10 ⁇ m.
  • the open porosity has a value in a range of ⁇ 10% by volume to ⁇ 30% by volume.
  • the open porosity of the material is the sum of the cavities that communicate with each other and with the environment, and is also referred to as Nutzporostician. As a result, a high thermal shock resistance is achieved at the same time sufficient stability.
  • the spinel ceramic is produced as a substantially isostatically pressed molding or produced by a plasma coating process. It is possible to apply the spinel ceramic to the substrate by means of the plasma coating process, comparable to a rapid prototyping process in several layers. This allows the spinel ceramic to be applied to a substrate that is easier to install to line the evaporation space. If necessary, a plurality of spinel ceramic layers can be provided one above the other, so that during a revision, one or more of the upper layers can be separated from an underlying layer in order to provide a uniform unused surface.
  • the different layers have a different composition and / or particle size distribution.
  • sufficient stability can be ensured, for example, in lower layers, whereas the upper layers are adapted to the measuring task.
  • Overall, an even better adaptation of the spinel ceramic to the measurement tasks is possible.
  • the vapor / CO 2 mixture obtained from the liquid sample to be measured by evaporation and oxidation is typically sent directly to the NDIR (Non-Dispersive) via an outlet port located on the furnace housing defining the evaporation space Infrared detector), via which the concentration of the resulting carbon dioxide is determined.
  • NDIR Non-Dispersive
  • Infrared detector Infrared detector
  • the spontaneous evaporation of the sample to be measured produces pulsed measuring signals at the detector. This correlates with the dripping frequency of the sample at the furnace inlet.
  • the amount of CO2 resulting from the sample thus flows frequently, pulsing past the NDIR detector. Accordingly, the detector determines not constant but highly fluctuating measured values, under which the measuring accuracy of the measuring system can suffer.
  • the high-temperature furnace according to the invention for T (O) C measurement may be modified such that the steam / CO 2 mixture is deflected by structural elements on the way within the evaporation space to the outlet opening.
  • the structural elements may be unattached in the evaporation space by touching each other.
  • the structural elements may be variably mounted by horizontal and / or vertical elevations in the evaporation space of the high-temperature furnace.
  • the constructive elements may be attached to the inner wall of the evaporation space.
  • the constructive elements can also be fastened to one another. In this case, different structural elements can be combined. It is also possible to combine fastened and unpaved constructional elements, both when they are of the same or different shape.
  • the interconnected cavities created by the structural elements act as buffer volumes. As a result, the pressure fluctuations on the way within the evaporation space via the outlet opening to the NDIR are compensated.
  • the constructive elements may be, for example, three-dimensional bodies, such as spheres, cuboids, rings, cones or cylinders or any other shaped three-dimensional body. Other structural elements such as straight or curved plates, struts or other flat elements may also be used.
  • the constructive elements may consist of different materials.
  • the structural elements are preferably made of or coated with spinel ceramic.
  • the structural elements are particularly preferably made of or coated with the same spinel ceramic as used to line the evaporation space of the high-temperature furnace for T (O) C measurement.
  • Another effect of this constructive change is that by diverting the vapor / CO 2 mixture non-vaporizable components, usually inorganic salts, which are formed during the oxidation of the sample or contained in the sample, are preferably retained in the evaporation chamber and not go to the outlet and continue to the NDIR. As a result, maintenance intervals of the entire analysis device are additionally increased and thus reduced operating costs.
  • the invention further relates to a use of a spinel ceramic for lining an evaporation space of a high-temperature furnace for T (O) C measurement of a sample, the high-temperature furnace in particular as described above and further educated.
  • the spinel ceramic is preferably formed and refined as described above with reference to the high temperature furnace. Due to the spinel ceramic, the evaporation space is lined by a material that allows particularly high temperatures within the evaporation space and thus the most complete combustion and at the same time is very resistant to thermal shock.
  • the invention further relates to a method for carrying out T (O) C measurements of samples, in which provision is made of a high-temperature furnace, wherein the high-temperature furnace has an evaporation chamber lined with a spinel ceramic.
  • the high-temperature furnace is in particular as described above and further developed.
  • the evaporation space is heated to operating temperature and a sample is introduced into the evaporation space.
  • a flushing liquid is introduced into the evaporation space substantially at the operating temperature for the removal of inorganic salts which have been recrystallized within the evaporation space from the sample.
  • the method can in particular be designed and developed further as described above with reference to the high-temperature furnace. Due to the spinel ceramic, the evaporation space is lined by a material that allows particularly high temperatures within the evaporation space and thus the most complete combustion and at the same time is very resistant to thermal shock. This makes it possible to substantially clean the evaporation space at operating temperature with a rinsing liquid and dissolved salts, in particular recrystallized inorganic salts from the evaporation space dissolved in the rinsing liquid or to remove undissolved. An aging of the high-temperature furnace by deposited salts can be avoided or at least significantly delayed.
  • a method for TOC measurement of samples comprising the steps of providing a high-temperature furnace, wherein the high-temperature furnace has a spinel-lined evaporation chamber, heating the evaporation space to operating temperature, introducing a sample into the evaporation space, evaporating and / or oxidizing the sample in the vaporizing space, measuring the amount of CO 2 produced, and introducing a rinsing liquid into the vaporizing space substantially at the operating temperature to remove inorganic salts recrystallized within the vaporizing space from the sample.
  • the rinsing liquid is injected into the evaporation space as an aerosol mist.
  • the rinsing liquid can thereby be introduced as mist or vapor and sprayed at a corresponding pressure against the respective rinsing opening opposite region of the spinel ceramic.
  • the rinsing liquid can more easily detach from the baked salts by the impact pressure that can be achieved thereby on the spinel ceramic.
  • a multiplicity of flushing openings is preferably uniformly distributed in the circumferential direction at a substantially common vertical height.
  • the evaporation space is dried essentially at operating temperature and subsequently another sample for T (O) C measurement is introduced into the evaporation space.
  • rinsing liquid water can be used.
  • organic, in particular carbonaceous, solvent as rinsing liquid.
  • CO 2 measurement can be determined when the rinse liquid is completely evaporated and removed from the evaporation chamber. Contamination of the T (O) C measurement by residues of the rinsing liquid remaining in the evaporation space is thereby avoided.
  • An operating temperature T O of 500 ° C. ⁇ T O ⁇ 2000 ° C., in particular 800 ° C. ⁇ T O ⁇ 1700 ° C., preferably 1000 ° C. ⁇ T O ⁇ 1500 ° C. and particularly preferably 1200 ° C. ⁇ T is particularly preferred O ⁇ 1300 ° C set.
  • substantially complete oxidation of the carbon can be achieved without risking material damage in the spinel ceramic due to temperature effects.
  • the operating costs can be further reduced.
  • the use of catalyst balls can be reduced by means of an internal predetermined, constructive gas path.
  • the same operating temperature is regulated immediately after the introduction of the sample and immediately after the introduction of the rinsing liquid as the target variable.
  • the temperature control of the high-temperature furnace does not have to differentiate between a normal operation and a flushing operation, so that the control is simplified.
  • unsteady temperature effects for example by heat conduction, can be avoided or at least significantly reduced, since interim cooling and heating as well as waiting until reaching a stationary operating state are avoided.
  • the stability and thermal shock resistance of the spinel ceramic is also caused by their chemical constitution.
  • the formulation of the spinel ceramic used can combine the properties of an oxide and a non-oxide ceramic by a suitable choice of the ceramic components.
  • oxide ceramics are harder, more wear-resistant and heat-resistant, but also more brittle than hard metals.
  • Non-oxide ceramics, such as nitrides, carbides or borides, for example, are characterized by high chemical and thermal stability, hardness and strength compared to oxide ceramics, however, accompanied by low ductility and quite high brittleness, caused by higher covalent and lower ionic bond fractions and thus by the strong binding energies. Therefore, the selection of modified spinel ceramics is possible. For example, in the case of a MgAl 2 O 4 ceramic, additional alumina or magnesium oxide may be added to obtain, for example, an Al 2 O 3 -rich or MgO-rich spinel ceramic.

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  • Engineering & Computer Science (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Health & Medical Sciences (AREA)
  • Clinical Laboratory Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Catalysts (AREA)

Claims (15)

  1. Four à haute température pour la mesure du C(O)T dans un échantillon, comportant
    une enceinte de four limitant une chambre de vaporisation, et qui présente une ouverture à échantillon pour l'introduction de l'échantillon goutte à goutte,
    caractérisé en ce que l'enceinte de four est revêtue d'une céramique de type spinelle sur une face intérieure tournée vers la chambre de vaporisation et présente au moins une ouverture de rinçage pour l'introduction d'un liquide de rinçage.
  2. Four à haute température selon la revendication 1, caractérisé en ce que l'ouverture de rinçage est raccordée à au moins une buse d'injection pour l'introduction d'un nuage d'aérosol en liquide de rinçage, ladite au moins une buse d'injection présentant une direction d'introduction orientée de façon essentiellement horizontale.
  3. Four à haute température selon l'une des revendications 1 ou 2, caractérisé en ce que la céramique de type spinelle comprend au moins une substance d'addition, qui est sélectionnée parmi les agents liquéfiants, les fibres céramiques ou d'autres matières de charge inorganiques.
  4. Four à haute température selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la céramique de type spinelle présente une distribution de la taille des grains discontinue.
  5. Four à haute température selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la céramique de type spinelle présente des pores, qui présentent une taille dans la plage ≤ 10 µm.
  6. Four à haute température selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la céramique de type spinelle présente une porosité ouverte dans une plage de ≥ 10 % en volume à ≤ 30 % en volume.
  7. Four à haute température selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la céramique de type spinelle est fabriquée sous la forme d'une pièce moulée par compression essentiellement isostatique ou est fabriquée par un procédé de dépôt au plasma.
  8. Four à haute température selon la revendication 7, caractérisé en ce que la céramique de type spinelle présente des couches différentes avec une composition et/ou une distribution de la taille des grains différente(s).
  9. Four à haute température selon l'une quelconque des revendications 1 à 8, caractérisé en ce que des éléments de construction sont placés à l'intérieur de l'enceinte de four, qui dévient le mélange vapeur/CO2 produit dans le four à haute température sur le chemin à l'intérieur de la chambre de vaporisation vers l'ouverture de sortie, les éléments de construction étant sélectionnés dans le groupe des corps tridimensionnels.
  10. Utilisation d'une céramique de type spinelle pour revêtir une chambre de vaporisation d'un four à haute température selon l'une quelconque des revendications 1 à 9 pour la mesure du C(O)T d'un échantillon.
  11. Procédé pour effectuer des mesures du C(O)T d'un échantillon, comprenant les étapes suivantes:
    préparer un four à haute température selon l'une quelconque des revendications 1 à 9, le four à haute température comportant une chambre de vaporisation revêtue d'une céramique de type spinelle,
    chauffer la chambre de vaporisation à la température de fonctionnement,
    introduire un échantillon dans la chambre de vaporisation,
    vaporiser et/ou oxyder l'échantillon dans la chambre de vaporisation,
    mesurer la quantité de CO2 produite,
    introduire un liquide de rinçage dans la chambre de vaporisation essentiellement à la température de fonctionnement pour éliminer les sels inorganiques provenant de l'échantillon recristallisés à l'intérieur de la chambre de vaporisation.
  12. Procédé selon la revendication 11, dans lequel on injecte le liquide de rinçage dans la chambre de vaporisation sous la forme d'un nuage d'aérosol.
  13. Procédé selon la revendication 11 ou 12, dans lequel on sèche la chambre de vaporisation essentiellement à la température de fonctionnement après l'élimination des sels inorganiques et on introduit ensuite un autre échantillon dans la chambre de vaporisation pour la mesure du C(O)T.
  14. Procédé selon l'une quelconque des revendications 11 à 13, dans lequel on règle une température de fonctionnement TO de 500°C≤TO≤2000°C, en particulier de 800°C≤TO≤1700°C, de préférence de 1000°C≤TO≤1500°C, et de préférence encore de 1200°C≤TO≤1300°C.
  15. Procédé selon l'une quelconque des revendications 11 à 14, dans lequel on régule la même température de fonctionnement comme grandeur cible immédiatement après l'introduction de l'échantillon et immédiatement après l'introduction du liquide de rinçage.
EP11748415.4A 2010-08-27 2011-08-26 Four haute température, utilisation d'une céramique de type spinelle et procédé permettant d'effectuer des mesures du c(o)t dans des échantillons Not-in-force EP2609388B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11748415.4A EP2609388B1 (fr) 2010-08-27 2011-08-26 Four haute température, utilisation d'une céramique de type spinelle et procédé permettant d'effectuer des mesures du c(o)t dans des échantillons

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10174403A EP2423627A1 (fr) 2010-08-27 2010-08-27 Four à température élevée, utilisation d'une céramique spinelle et procédé d'exécution de mesures T(O)C d'échantillons
PCT/EP2011/064698 WO2012025611A1 (fr) 2010-08-27 2011-08-26 Four haute température, utilisation d'une céramique de type spinelle et procédé permettant d'effectuer des mesures du c(o)t dans des échantillons
EP11748415.4A EP2609388B1 (fr) 2010-08-27 2011-08-26 Four haute température, utilisation d'une céramique de type spinelle et procédé permettant d'effectuer des mesures du c(o)t dans des échantillons

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EP2609388A1 EP2609388A1 (fr) 2013-07-03
EP2609388B1 true EP2609388B1 (fr) 2015-01-07

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EP10174403A Withdrawn EP2423627A1 (fr) 2010-08-27 2010-08-27 Four à température élevée, utilisation d'une céramique spinelle et procédé d'exécution de mesures T(O)C d'échantillons
EP11748415.4A Not-in-force EP2609388B1 (fr) 2010-08-27 2011-08-26 Four haute température, utilisation d'une céramique de type spinelle et procédé permettant d'effectuer des mesures du c(o)t dans des échantillons

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EP (2) EP2423627A1 (fr)
CN (1) CN103080683A (fr)
WO (1) WO2012025611A1 (fr)

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JP6631817B2 (ja) 2018-03-30 2020-01-15 株式会社エコロ Ｔｏｃ計測方法及びそれに使用するｔｏｃ計測装置

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US4078894A (en) * 1976-11-12 1978-03-14 Raytheon Company Analyzer system with salt extractor
DE4417247B4 (de) * 1994-05-17 2006-06-08 Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG Verbrennungsofen für Flüssigkeitsproben
CN2826430Y (zh) * 2005-08-19 2006-10-11 徐滋秋 实验室总有机碳测定仪
CN2856999Y (zh) * 2005-12-12 2007-01-10 叶大林 水的总有机碳（toc）测定仪
CN101241067A (zh) * 2008-03-14 2008-08-13 赵双平 总有机碳总氮联测仪
DE102008025877A1 (de) * 2008-05-29 2009-12-03 Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG Vorrichtung zur Bestimmung des Gehalts an mindestens einem oxidierbaren Inhaltsstoff in einer wässrigen Flüssigkeitsprobe
CN201488944U (zh) * 2009-08-10 2010-05-26 重庆川仪自动化股份有限公司 一种总有机碳(toc)分析仪
CN101776606A (zh) * 2010-02-05 2010-07-14 江苏扬农化工集团有限公司 一种对液体中总碳和总有机碳进行分析的方法

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EP2609388A1 (fr) 2013-07-03
CN103080683A (zh) 2013-05-01
WO2012025611A1 (fr) 2012-03-01
EP2423627A1 (fr) 2012-02-29

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