ES2582495B1 - IDENTIFICATION EQUIPMENT FOR MERCURY SPECIES IN SOLIDS - Google Patents
IDENTIFICATION EQUIPMENT FOR MERCURY SPECIES IN SOLIDS Download PDFInfo
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- ES2582495B1 ES2582495B1 ES201530310A ES201530310A ES2582495B1 ES 2582495 B1 ES2582495 B1 ES 2582495B1 ES 201530310 A ES201530310 A ES 201530310A ES 201530310 A ES201530310 A ES 201530310A ES 2582495 B1 ES2582495 B1 ES 2582495B1
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- 239000007787 solid Substances 0.000 title claims abstract description 38
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 61
- 239000007789 gas Substances 0.000 claims abstract description 23
- 238000003795 desorption Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 10
- 150000002731 mercury compounds Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001081 sequentional extraction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4022—Concentrating samples by thermal techniques; Phase changes
-
- 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
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0045—Hg
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Muffle Furnaces And Rotary Kilns (AREA)
Abstract
Equipo de identificación de especies de mercurio en sólidos mediante desorción térmica que permite analizar muestras sólidas y comprende una entrada de la muestra sólida (1), un horno comercial (2), un analizador (4) y una unidad de control (5). Comprende también un horno adicional (6) que está conectado por una primera cámara (7) a la entrada de la muestra sólida (1) y por una segunda cámara (8) al horno comercial (2). El equipo dispone de una primera entrada de gases (9) para gas inerte dispuesta en el horno adicional (6), y una segunda entrada de gases (10) para aire u oxígeno dispuesta en el horno comercial (2). El equipo comprende también un primer controlador de temperatura en la primera cámara (7) del horno adicional, y un segundo controlador de temperatura en la segunda cámara (8) del horno adicional.Equipment for the identification of mercury species in solids by means of thermal desorption that allows solid samples to be analyzed and comprises a solid sample inlet (1), a commercial oven (2), an analyzer (4) and a control unit (5). It also includes an additional oven (6) that is connected by a first chamber (7) to the entrance of the solid sample (1) and by a second chamber (8) to the commercial oven (2). The equipment has a first gas inlet (9) for inert gas disposed in the additional furnace (6), and a second gas inlet (10) for air or oxygen arranged in the commercial furnace (2). The equipment also comprises a first temperature controller in the first chamber (7) of the additional oven, and a second temperature controller in the second chamber (8) of the additional oven.
Description
EQUIPO DE IDENTIFICACION DE ESPECIES DE MERCURIO EN SOLIDOSIDENTIFICATION TEAM OF MERCURY SPECIES IN SOLIDS
D E S C R I P C I OND E S C R I P C I ON
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OBJETO DE LA INVENCIONOBJECT OF THE INVENTION
La presente invention se enmarca en el campo tecnico del analisis de especies de mercurio en muestras solidas.The present invention is part of the technical field of the analysis of mercury species in solid samples.
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El equipo descrito permite determinar las especies de mercurio en productos derivados de la combustion y conversion del carbon y de cualquier combustible que tenga materia carbonosa, y en general, de cualquier solido contaminado con mercurio.The described equipment allows to determine the species of mercury in products derived from the combustion and conversion of carbon and any fuel that has carbonaceous matter, and in general, of any solid contaminated with mercury.
15 ANTECEDENTES DE LA INVENCION15 BACKGROUND OF THE INVENTION
La identification y cuantificacion de compuestos organicos e inorganicos de mercurio en muestras es un campo de estudio muy importante en la actualidad ya que se trata de un elemento quimico muy contaminante que ademas puede resultar muy danino para el ser 20 humano.The identification and quantification of organic and inorganic mercury compounds in samples is a very important field of study at present because it is a very polluting chemical element that can also be very harmful for humans.
Para realizar dicha determination se conocen diferentes tecnicas con sus correspondientes ventajas y desventajas. Asi pues, se conoce por ejemplo la espectrometria de absorcion de rayos X, que esta basada en la diferente absorcion de 25 atomos en funcion de sus atomos vecinos. Con esta tecnica se pueden obtener espectros caracteristicos de cada compuesto pero no se alcanzan Kmites de detection bajos. Ademas en muchos casos este metodo presenta interferencias y el tratamiento de datos es complejo.To perform this determination, different techniques are known with their corresponding advantages and disadvantages. Thus, for example, the X-ray absorption spectrometry is known, which is based on the different absorption of 25 atoms depending on their neighboring atoms. With this technique characteristic spectra of each compound can be obtained but low detection limits are not reached. In many cases, this method also interferes and the data processing is complex.
30 Se conoce tambien la tecnica de extraction quimica secuencial, que permite separar las especies de mercurio en funcion de su solubilidad en distintos disolventes empleados secuencialmente. Los problemas tecnicos asociados a esta tecnica son consecuencia de a) que tiene una selectividad baja debido a que la extraccion completa de cada fraccion depende del tiempo, b) que no diferencia entre todas las especies de mercurio y c) que30 The technique of sequential chemical extraction is also known, which allows mercury species to be separated based on their solubility in different solvents used sequentially. The technical problems associated with this technique are a consequence of a) that it has a low selectivity because the complete extraction of each fraction depends on the time, b) that does not differentiate between all the species of mercury and c) that
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se trata de un metodo tedioso con numerosas fuentes de incertidumbre.It is a tedious method with numerous sources of uncertainty.
Otra tecnica conocida para la identification de las especies de mercurio es la basada en la desorcion termica, que es la que emplea el equipo de la presente invention. Esta tecnica se emplea generalmente para la determination de mercurio total en solidos y no para la identificacion de especies de mercurio. La identificacion de las especies de mercurio se realiza en funcion de su temperatura de desorcion, de forma que cuando se lleva a cabo la desorcion bajo temperatura controlada se obtienen picos de temperatura caracteristicos de cada compuesto. Esta tecnica ha sido empleada para identificar compuestos de mercurio en distintos tipos de muestras, como por ejemplo, en suelos contaminados, sedimentos y materia particulada de aerosoles. Para poder identificar los compuestos de mercurio es necesaria la preparation de compuestos estandar de mercurio con los que elaborar una base de datos y asi poder asignar un pico de temperatura para cada uno de los compuestos de mercurio presentes en los solidos.Another known technique for the identification of mercury species is that based on thermal desorption, which is the one used by the equipment of the present invention. This technique is generally used for the determination of total mercury in solids and not for the identification of mercury species. The identification of mercury species is carried out according to their desorption temperature, so that when the desorption is carried out under controlled temperature, characteristic temperature peaks of each compound are obtained. This technique has been used to identify mercury compounds in different types of samples, such as contaminated soils, sediments and aerosol particulate matter. In order to identify mercury compounds, it is necessary to prepare standard mercury compounds with which to prepare a database and thus be able to assign a temperature peak for each of the mercury compounds present in solids.
Del estado de la tecnica se conoce por ejemplo el documento US5882381 que describe un sistema de desorcion termica para tratamiento de residuos solidos para eliminar residuos con mercurio. Se realiza una desorcion termica de los elementos contaminantes y el proceso se lleva a cabo en una atmosfera de gas inerte. Esta disenado para el tratamiento en continuo de los residuos solidos.From the state of the art, for example, document US5882381 is known which describes a thermal desorption system for solid waste treatment to eliminate residues with mercury. A thermal desorption of the polluting elements is carried out and the process is carried out in an atmosphere of inert gas. It is designed for the continuous treatment of solid waste.
Se conoce tambien un metodo y el equipo para implementarlo, tal y como se describe en US7048779, para eliminar mercurio de los gases producidos en las plantas de production de energia a partir de carbon. El equipo comprende un dispositivo de recogida de particulas de mayor tamano, un filtro para particulas mas finas, una fuente de carbon para introducir carbon activado en polvo, una unidad de desorcion para separar dicho carbon activado del mercurio que esta contenido en el y una salida de recirculation del carbon ya limpio.It is also known a method and the equipment to implement it, as described in US7048779, to remove mercury from the gases produced in the plants producing energy from carbon. The equipment comprises a device for collecting larger particles, a filter for finer particles, a source of carbon to introduce activated carbon powder, a desorption unit for separating said activated carbon from the mercury contained in it and an outlet of recirculation of carbon already clean.
En el documento US2012205533 se describe un sistema y un metodo para medir cuantitativamente multiples especies de metales pesados que incluyen mercurio u otros contaminantes toxicos. Las muestras que se pueden analizar con este sistema y este metodo son de agua, aire, Kquido, hielo y nieve.US2012205533 describes a system and method for quantitatively measuring multiple species of heavy metals that include mercury or other toxic contaminants. The samples that can be analyzed with this system and this method are water, air, liquid, ice and snow.
Los equipos actualmente conocidos basados en la desorcion termica para identification de especies de mercurio en muestras solidas tienen los siguientes problemas tecnicos asociados:Currently known equipment based on thermal desorption for the identification of mercury species in solid samples have the following associated technical problems:
-no se pueden emplear con muestras de carbones,-cannot be used with carbon samples,
5 -es necesario optimizar las variables que afectan al ensanchamiento o5 -It is necessary to optimize the variables that affect the widening or
solapamiento de picos,overlapping peaks,
-es necesario eliminar posibles interferencias (la elevada concentration de materia organica en los carbones puede interferir en la senal obtenida).-It is necessary to eliminate possible interference (the high concentration of organic matter in the coals can interfere with the signal obtained).
10 DESCRIPCION DE LA INVENCION10 DESCRIPTION OF THE INVENTION
La presente invention describe un equipo de identificacion de especies de mercurio en solidos que permite resolver los problemas tecnicos asociados a los equipos de desorcion termica del estado de la tecnica.The present invention describes a team for the identification of mercury species in solids that allows solving the technical problems associated with thermal desorption equipment of the state of the art.
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Se trata de un equipo de detection de especies de mercurio en solidos que comprende al menos una entrada para la muestra solida, dos hornos con control de temperatura, un analizador y una unidad de control para gestionar todos los datos obtenidos de senal de mercurio, temperaturas, flujo, etc. El equipo comprende un horno comercial y un horno 20 adicional. El horno adicional esta formado por dos camaras: una primera camara por la que se introduce la muestra solida y esta se descompone a temperatura controlada, y una segunda camara que permite la conexion con el horno comercial, evitando la perdida de calor. Ambas camaras del horno adicional son dos zonas diferenciadas del horno que estan rodeadas de hilo de resistencia 0.65 mm (0) que permite alcanzar altas 25 temperaturas de forma rapida y evita problemas de oxidation. Cada uno de los hilos esta conectado a un correspondiente controlador de temperatura que permite que la primera camara y la segunda camara se calienten a temperaturas distintas. Asimismo el equipo comprende una primera entrada de gas a traves de la cual se introduce en el equipo un gas inerte y que esta conectada al horno adicional. El equipo comprende tambien una 30 segunda entrada de gas a traves de la cual se introduce aire u oxigeno, y que esta conectada al horno comercial.It is a team for the detection of mercury species in solids that includes at least one input for the solid sample, two ovens with temperature control, an analyzer and a control unit to manage all the data obtained from mercury signal, temperatures , flow, etc. The equipment comprises a commercial oven and an additional oven 20. The additional oven is formed by two chambers: a first chamber through which the solid sample is introduced and it decomposes at a controlled temperature, and a second chamber that allows the connection with the commercial oven, avoiding heat loss. Both cameras of the additional oven are two differentiated zones of the oven that are surrounded by 0.65 mm (0) resistance wire that allows to reach high temperatures quickly and avoids oxidation problems. Each of the wires is connected to a corresponding temperature controller that allows the first chamber and the second chamber to heat to different temperatures. The equipment also comprises a first gas inlet through which an inert gas is introduced into the equipment and is connected to the additional furnace. The equipment also comprises a second gas inlet through which air or oxygen is introduced, and which is connected to the commercial oven.
El equipo comprende un primer controlador de temperatura en la primera camara del horno adicional , que es el elemento encargado de regular las rampas de temperaturaThe equipment comprises a first temperature controller in the first chamber of the additional oven, which is the element responsible for regulating the temperature ramps
que se aplican a la muestra solida, y un segundo controlador de temperatura que esta dispuesto en la segunda camara que se encarga de regular la temperatura para que se produzca una correcta transferencia de calor manteniendo la temperatura entre el horno adicional y el horno comercial y asi evitar perdidas en el registro de la senal de mercurio.which are applied to the solid sample, and a second temperature controller that is arranged in the second chamber that regulates the temperature so that a proper heat transfer occurs while maintaining the temperature between the additional oven and the commercial oven and thus avoid losses in the mercury signal register.
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El equipo permite identificar especies de mercurio en matrices carbonosas sin que la presencia de la materia organica de los carbones interfiera en la senal recogida en el detector de mercurio y tambien permite evaluar la influencia de diferentes rampas de calentamiento en la sensibilidad y selectividad de las curvas de desorcion obtenidas con 10 los compuestos puros de mercurio.The equipment allows to identify species of mercury in carbonaceous matrices without the presence of the organic matter of the coals interfering with the signal collected in the mercury detector and also allows to evaluate the influence of different heating ramps on the sensitivity and selectivity of the curves of desorption obtained with 10 pure mercury compounds.
La incorporation del horno adicional formado por dos camaras permite una mejor variation del numero y tipo de rampas de temperatura aplicables.The incorporation of the additional oven formed by two chambers allows a better variation of the number and type of applicable temperature ramps.
15 En el horno adicional se produce la desorcion (que es la descomposicion de las especies de mercurio). Este horno adicional esta conectado a la entrada de la muestra, que preferentemente se introduce en una navecilla de cuarzo, y tambien a la primera entrada de gas, que es por donde se introduce un gas portador inerte, que preferentemente es Ar o N2 para que la descomposicion se produzca sin que haya ninguna transformation. Para 20 controlar el horno adicional se emplea un programa de control que permite crear curvas de temperatura entre 25 y 700°C. Descomponer las especies de mercurio a temperatura controlada permite correlacionar cada especie de mercurio con su temperatura caracteristica de desorcion.15 Desorption occurs in the additional furnace (which is the decomposition of mercury species). This additional oven is connected to the sample inlet, which is preferably introduced in a quartz boat, and also to the first gas inlet, which is where an inert carrier gas is introduced, which is preferably Ar or N2 so that Decomposition occurs without any transformation. To control the additional oven, a control program is used to create temperature curves between 25 and 700 ° C. Decomposing mercury species at a controlled temperature allows each species of mercury to be correlated with its characteristic desorption temperature.
25 Cuando la especie de mercurio se libera del solido sin haber sufrido ninguna transformacion pasa al horno comercial. A este horno comercial esta conectada la segunda entrada de gas (por la que entra aire u oxigeno). En un ejemplo de realization la temperatura del horno comercial se mantiene fija a 800°C. En el horno comercial se queman los compuestos organicos de la muestra y el mercurio oxidado se reduce a Hg0 30 para posteriormente pasar hasta el analizador de mercurio donde es determinado. En este horno comercial, por tanto, se produce una descomposicion total de la muestra para que pueda ser determinada.25 When the species of mercury is released from the solid without having undergone any transformation, it goes into the commercial oven. The second gas inlet (through which air or oxygen enters) is connected to this commercial oven. In an example of realization the temperature of the commercial oven is kept fixed at 800 ° C. In the commercial oven, the organic compounds of the sample are burned and the oxidized mercury is reduced to Hg0 30 and then passed to the mercury analyzer where it is determined. In this commercial oven, therefore, a total decomposition of the sample occurs so that it can be determined.
Un problema que puede surgir de la disposition de componentes descrita es que lasA problem that may arise from the provision of components described is that the
especies de mercurio sean arrastradas en una corriente de nitrogeno en el interior del horno comercial. Esto puede provocar errores en la determination cuantitativa del mercurio debido a que las especies de mercurio pueden reaccionar con algun componente del equipo produciendo corrosion y errores analrticos. Para solucionar este 5 problema el equipo de la invention comprende un tubo interno, que es preferentemente de cuarzo, que atraviesa el horno adicional y el horno comercial y los conecta. Ademas este tubo interno permite evitar la corrosion y evitar perdidas de mercurio entre los hornos.Mercury species are carried in a stream of nitrogen inside the commercial oven. This can cause errors in the quantitative determination of mercury because mercury species can react with some component of the equipment causing corrosion and analrtic errors. To solve this problem, the equipment of the invention comprises an internal tube, which is preferably quartz, which crosses the additional oven and the commercial oven and connects them. In addition, this inner tube allows to avoid corrosion and avoid losses of mercury between the furnaces.
10 Otro problema tecnico a resolver es la regulation de la transferencia de calor desde el horno adicional hasta el horno comercial porque esta transferencia de calor puede no producirse de manera homogenea. Para ello el equipo propuesto comprende un segundo controlador de temperatura que esta dispuesto en la segunda camara del horno adicional. Este segundo controlador de temperatura esta coordinado con la primera 15 camara del horno adicional y con el horno comercial para garantizar la transferencia de calor controlada entre ellos.10 Another technical problem to solve is the regulation of heat transfer from the additional furnace to the commercial furnace because this heat transfer may not occur homogeneously. For this, the proposed equipment comprises a second temperature controller that is arranged in the second chamber of the additional oven. This second temperature controller is coordinated with the first 15 chamber of the additional oven and the commercial oven to ensure controlled heat transfer between them.
Respecto a la segunda entrada de gases, que es por donde se introducen oxigeno o aire, esta se ha dispuesto directamente en el tubo de cuarzo en el horno comercial para evitar 20 que haya perdidas de mercurio y permitir un correcto analisis cuantitativo de la muestra.Regarding the second inlet of gases, which is where oxygen or air are introduced, it has been placed directly in the quartz tube in the commercial oven to avoid the loss of mercury and allow a correct quantitative analysis of the sample.
Otro problema a resolver por el equipo de la presente invencion es que sea versatil y permita el analisis de las especies de mercurio de forma precisa, sencilla y rapida. En concreto para que el equipo funcione de forma rapida se ha introducido un ventilador en 25 el horno adicional que permite reducir el tiempo de espera del analisis de 5 horas a 3 horas.Another problem to be solved by the team of the present invention is that it is versatile and allows the analysis of mercury species accurately, simply and quickly. In particular, in order for the equipment to work quickly, a fan has been introduced in the additional oven, which allows the waiting time of the analysis to be reduced from 5 hours to 3 hours.
Con este equipo se consigue desdoblar la senal en varios picos perfectamente diferenciados mejorando la selectividad de las tecnicas de desorcion termica que permite 30 identificar mas especies de mercurio de las que serian identificables con los dispositivos conocidos del estado de la tecnica.With this equipment, the signal can be split into several perfectly differentiated peaks, improving the selectivity of thermal desorption techniques, which allows the identification of more mercury species than would be identifiable with the devices known in the state of the art.
Ademas el equipo para detection de especies de mercurio en solidos de la presente invencion puede ser usado para el analisis de todo tipo de muestras solidas y enIn addition the equipment for detection of mercury species in solids of the present invention can be used for the analysis of all types of solid samples and in
particular para los productos y subproductos derivados de la combustion y conversion del carbon. Tambien se obtienen buenos resultados al analizar cualquier tipo de combustible que contenga materia carbonosa. Conocer las especies de mercurio presentes en los diferentes solidos de una central termica permite conocer el comportamiento del mercurio 5 durante todo el proceso y determinar el riesgo de los residuos y subproductos generados.particular for products and by-products derived from the combustion and conversion of carbon. Good results are also obtained when analyzing any type of fuel that contains carbonaceous matter. Knowing the species of mercury present in the different solids of a thermal power plant allows to know the behavior of mercury 5 during the whole process and determine the risk of the waste and by-products generated.
Asimismo con el equipo de la presente invention se pueden estudiar solidos empleados como absorbentes de mercurio en procesos de production de energia, lo cual, teniendo en cuenta que la combustion de carbon es una de las principales fuentes de mercurio al 10 medioambiente, es necesario controlar las cantidades de este elemento.Likewise, with the equipment of the present invention, solids used as mercury absorbers in energy production processes can be studied, which, taking into account that the combustion of carbon is one of the main sources of mercury in the environment, it is necessary to control The quantities of this item.
El equipo se puede usar con cualquier producto contaminado por mercurio ya que el destino, el transporte y la biodisponibilidad de los materiales van a depender de las especies presentes.The equipment can be used with any product contaminated by mercury since the destination, transport and bioavailability of the materials will depend on the species present.
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DESCRIPCION DE LOS DIBUJOSDESCRIPTION OF THE DRAWINGS
Para complementar la description que se esta realizando y con objeto de ayudar a una mejor comprension de las caracteristicas de la invencion, de acuerdo con un ejemplo 20 preferente de realization practica de la misma, se acompana como parte integrante de dicha descripcion, un juego de dibujos en donde con caracter ilustrativo y no limitativo, se ha representado lo siguiente:To complement the description that is being made and in order to help a better understanding of the features of the invention, according to a preferred example of practical realization thereof, a set of said description is attached, as an integral part of said description. Drawings where the following has been illustrated and not limited to:
Figura 1.- Muestra una vista completa del equipo de la presente invencion.Figure 1.- Shows a complete view of the equipment of the present invention.
2525
Figura 2.- Muestra una vista en detalle de las camaras y los hornos del equipo.Figure 2.- Shows a detailed view of the chambers and ovens of the equipment.
Figura 3a.- Muestra una representation de los resultados obtenidos de identification de especies de mercurio en una muestra solida de carbon con un equipo conocido del 30 estado de la tecnica.Figure 3a.- Shows a representation of the results obtained from the identification of mercury species in a solid carbon sample with a known equipment of the prior art.
Figura 3b.- Muestra una representacion de los resultados obtenidos de identificacion de especies de mercurio en una muestra solida de carbon con el equipo de la presente invencion.Figure 3b.- Shows a representation of the results obtained from the identification of mercury species in a solid carbon sample with the equipment of the present invention.
REALIZACION PREFERENTE DE LA INVENCIONPREFERRED EMBODIMENT OF THE INVENTION
5 A continuation se describe, con ayuda de las figuras 1 a 3, un ejemplo de realization5 An example of realization is described below with the help of Figures 1 to 3
de la presente invention.of the present invention.
El equipo de identification de especies de mercurio en muestras solidas propuesto emplea la tecnica de la desorcion termica. Para ello el equipo comprende al menos 10 una entrada de la muestra solida (1), un horno comercial (2) con un controlador de temperatura del horno comercial (3), un analizador (4) y una unidad de control (5) configurada para controlar el equipo.The team of identification of species of mercury in solid samples proposed uses the technique of thermal desorption. For this, the equipment comprises at least 10 a solid sample inlet (1), a commercial oven (2) with a commercial oven temperature controller (3), an analyzer (4) and a control unit (5) configured To control the equipment.
Para poder obtener los buenos resultados de identificacion de mercurio descritos 15 anteriormente el equipo comprende ademas un horno adicional (6) que comprende una primera camara (7) y una segunda camara (8) dispuestas una a continuacion de la otra. Este horno adicional (6) esta conectado con la primera camara (7) a la entrada de la muestra solida (1) y con la segunda camara (8) al horno comercial (2). Como se ha descrito previamente, el horno adicional permite someter a la muestra a una mayor 20 variedad de curvas de temperatura en numero y tipo de curvas. Esto facilita la correlation de la especie de mercurio con su temperatura concreta de desorcion y por tanto mejora la precision de los resultados.In order to obtain the good mercury identification results described above, the equipment also comprises an additional oven (6) comprising a first chamber (7) and a second chamber (8) arranged next to each other. This additional oven (6) is connected with the first chamber (7) to the entrance of the solid sample (1) and with the second chamber (8) to the commercial oven (2). As described previously, the additional oven allows the sample to be subjected to a greater variety of temperature curves in number and type of curves. This facilitates the correlation of the mercury species with its specific desorption temperature and therefore improves the accuracy of the results.
El equipo comprende ademas dos entradas de gases de las cuales una primera entrada 25 de gases (9), a traves de la que pasa un gas inerte, esta dispuesta en el horno adicional (6), y una segunda entrada de gases (10), a traves de la que pasan aire u oxigeno, y que esta dispuesta en el horno comercial (2). El gas inerte se emplea para la desorcion del mercurio de la muestra en el horno adicional (6) evitando cualquier interferencia y el oxigeno se emplea para descomponer completamente la muestra en el horno comercial 30 (2).The equipment also comprises two gas inlets of which a first gas inlet 25 (9), through which an inert gas passes, is arranged in the additional furnace (6), and a second gas inlet (10) , through which air or oxygen passes through, and which is arranged in the commercial oven (2). The inert gas is used for desorption of the mercury from the sample in the additional oven (6) avoiding any interference and oxygen is used to completely decompose the sample in the commercial oven 30 (2).
El equipo dispone tambien de un primer controlador de temperatura (11) para la primera camara (7) del horno adicional (6) y un segundo controlador de temperatura (12) para la segunda camara (8) del horno adicional (6).The equipment also has a first temperature controller (11) for the first chamber (7) of the additional oven (6) and a second temperature controller (12) for the second chamber (8) of the additional oven (6).
Adicionalmente el equipo puede comprender una estacion de gases (13) con unas conexiones a las dos entradas de gases (9, 10) y que comprende dos controladores de flujo de gases (14) para cada conexion a las entradas de gases (9,10).Additionally, the equipment can comprise a gas station (13) with connections to the two gas inlets (9, 10) and comprising two gas flow controllers (14) for each connection to the gas inlets (9.10 ).
Para evitar posibles fugas de mercurio cuando este pasa del horno adicional al horno comercial el equipo comprende un tubo interno (15) que atraviesa el horno adicional (6) hasta el horno comercial (2) y los conecta entre si. Asi pues el mercurio pasa a traves del tubo sin que haya posibilidad de fugas y evitando la corrosion en el interior de los hornos 10 (6, 2). Preferentemente el tubo interno (15) es de cuarzo que es un material que resisteTo avoid possible leaks of mercury when it passes from the additional oven to the commercial oven the equipment comprises an internal tube (15) that passes through the additional oven (6) to the commercial oven (2) and connects them together. Thus, the mercury passes through the tube without any possibility of leakage and avoiding corrosion inside the furnaces 10 (6, 2). Preferably the inner tube (15) is made of quartz which is a material that resists
altas temperaturas.high temperatures.
Adicionalmente el equipo puede comprender una junta torica configurada para sellar la union entre el horno adicional y el horno comercial a traves del tubo interno (15) que evita 15 que haya perdidas de mercurio cuando se produce el paso del horno adicional al horno comercial. Asi se consigue que se queme bien toda la muestra y se puedan identificar las especies de mercurio y determinar la concentration total y de cada especie de mercurio.Additionally, the equipment can comprise a toric joint configured to seal the joint between the additional oven and the commercial oven through the inner tube (15) that prevents mercury from being lost when the additional oven passes to the commercial oven. This ensures that the entire sample is burned and the mercury species can be identified and the total concentration of each mercury species can be determined.
En la entrada de la muestra solida (1) un portamuestras con un termopar (16) esta 20 configurado para medir la temperatura de la muestra continuamente.At the entrance of the solid sample (1) a sample holder with a thermocouple (16) is configured to measure the temperature of the sample continuously.
En las figuras 3a y 3b se han representado los resultados obtenidos para la identification de especies de mercurio en una muestra solida de carbon empleando un equipo del estado de la tecnica (se muestra el resultado en la figura 3a) y empleando el equipo de la 25 presente invention (se muestra el resultado en la figura 3b). Como se aprecia a la vista de dichas graficas los datos obtenidos con un equipo del estado de la tecnica son menos precisos y selectivos. El equipo del estado de la tecnica no ha permitido la identificacion de varias especies de mercurio debido al solapamiento de la senal en un solo pico. Sin embargo al emplear el equipo de la presente invencion se ha aumentado la precision y 30 selectividad permitiendo la identificacion de especies de mercurio diferentes (representado en la grafica en modo de dos picos a temperatura diferente).Figures 3a and 3b show the results obtained for the identification of mercury species in a solid carbon sample using a state of the art equipment (the result is shown in figure 3a) and using the equipment of the present invention (the result is shown in Figure 3b). As can be seen in view of these graphs, the data obtained with a state of the art equipment are less precise and selective. The state-of-the-art team has not allowed the identification of several species of mercury due to signal overlap in a single peak. However, when using the equipment of the present invention, the accuracy and selectivity have been increased allowing the identification of different mercury species (represented in the graph in the form of two peaks at different temperatures).
Claims (7)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201530310A ES2582495B1 (en) | 2015-03-11 | 2015-03-11 | IDENTIFICATION EQUIPMENT FOR MERCURY SPECIES IN SOLIDS |
| PCT/EP2016/055198 WO2016142494A1 (en) | 2015-03-11 | 2016-03-10 | Equipment for identifying mercury species in solids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES201530310A ES2582495B1 (en) | 2015-03-11 | 2015-03-11 | IDENTIFICATION EQUIPMENT FOR MERCURY SPECIES IN SOLIDS |
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| ES201530310A Withdrawn - After Issue ES2582495B1 (en) | 2015-03-11 | 2015-03-11 | IDENTIFICATION EQUIPMENT FOR MERCURY SPECIES IN SOLIDS |
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| CN106442606B (en) * | 2016-09-28 | 2019-01-15 | 华中科技大学 | A kind of method and apparatus identifying mercury shape |
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| US8133303B2 (en) * | 2008-07-02 | 2012-03-13 | Schwab James J | Apparatus and method for controlling mercury pollution from a cement plant |
| WO2011020187A1 (en) * | 2009-08-19 | 2011-02-24 | Mcgill University | Methods and systems for the quantitative chemical speciation of heavy metals and other toxic pollutants |
| JP5001419B2 (en) * | 2010-11-30 | 2012-08-15 | 日本インスツルメンツ株式会社 | Heated combustion tube, pyrolysis device and mercury analyzer for mercury analysis |
| CN202661381U (en) * | 2012-04-12 | 2013-01-09 | 中国科学院城市环境研究所 | Thermal desorption and analysis device for different form mercury samples in atmosphere |
| CN204122456U (en) * | 2014-10-14 | 2015-01-28 | 中节能大地环境修复有限公司 | A kind of mercury contaminated soil thermal desorption treating apparatus |
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| ES2582495A1 (en) | 2016-09-13 |
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