WO2016142494A1 - Équipement d'identification d'espèce du mercure dans des solides - Google Patents

Équipement d'identification d'espèce du mercure dans des solides Download PDF

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Publication number
WO2016142494A1
WO2016142494A1 PCT/EP2016/055198 EP2016055198W WO2016142494A1 WO 2016142494 A1 WO2016142494 A1 WO 2016142494A1 EP 2016055198 W EP2016055198 W EP 2016055198W WO 2016142494 A1 WO2016142494 A1 WO 2016142494A1
Authority
WO
WIPO (PCT)
Prior art keywords
equipment
oven
chamber
mercury
mercury species
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.)
Ceased
Application number
PCT/EP2016/055198
Other languages
English (en)
Inventor
Marta RUMAYOR VILLAMIL
María Antonia LÓPEZ ANTÓN
Mercedes DÍAZ SOMOANO
Rosa MARTÍNEZ TARAZONA
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.)
Consejo Superior de Investigaciones Cientificas CSIC
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Consejo Superior de Investigaciones Cientificas CSIC filed Critical Consejo Superior de Investigaciones Cientificas CSIC
Publication of WO2016142494A1 publication Critical patent/WO2016142494A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
    • 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

Definitions

  • the present invention comes within the technical field of analysis of mercury species in solid samples.
  • the equipment described allows the mercury species to be identified in products derived from the combustion and conversion of coal and any fuel which has carbonaceous material, in general, any solid contaminated with mercury.
  • x-ray absorption spectroscopy which is based on the different absorption of atoms as a function of neighboring atoms.
  • characteristic spectrums of each compound can be obtained, but low detection limits are not reached.
  • this method is subject to interferences and the treatment of data is complex.
  • the sequential chemical extraction technique can be used. This allows the mercury species to be separated as a function of their solubility in different sequentially arranged solvents.
  • the technical problems associated with this technique are a result of the fact that a) it has a low selectivity as the complete extraction of each fraction depends on time, b) no distinction is made between the mercury species and c) it is a tedious method that entails numerous sources of uncertainty.
  • Another known technique for identifying mercury species is thermal desorption which is the method upon which the present invention is based. This technique is generally used for determining the total mercury content in solids rather than for identifying mercury species. Identifying the mercury species is carried out as a function of the desorption temperature thereof such that when the desorption is carried out under controlled temperature, temperature peaks characteristic of each compound are obtained. This method has been used to identify mercury compounds in different types of samples, such as contaminated soils, sediments and airborne particulate matter. In order to be able to identify the mercury compounds, it is necessary to prepare several reference samples of mercury compounds from which a database is created establishing a temperature peak to each mercury compound present in the solids.
  • US7048779 also describes a method and equipment for removing mercury from a coal fired power plant exhaust gas.
  • the equipment comprises a bulk particle filter to remove coarse particles, followed by the introduction of powdered activated carbon which is separated from the exhaust gas in a fine particle filter to enable subsequent elevated temperature desorption to separate the mercury and inert gas from the powdered activated carbon.
  • the present invention describes an equipment for identifying mercury species in solids that avoids the technical problems generally associated with state-of-the-art thermal desorption equipments.
  • the equipment for identifying mercury species in solids comprises at least one solid inlet for the solid sample, two ovens with temperature control, one analyzer and a control unit for processing all the data obtained including mercury signal, temperatures, flow rates, etc.
  • the equipment comprises a commercial oven, and an additional oven consisting of two chambers: a first chamber in which the solid sample is placed to undergo decomposition at a controlled temperature, and a second chamber connected to the commercial oven, to avoid loss of heat. Both chambers may be surrounded by a, for instance, 0.65 mm (0) resistance wire which allows high temperatures to be reached quickly and avoids oxidation problems. Each one of the wires is connected to a corresponding temperature controller which allows the first chamber and the second chamber to heat at different temperatures.
  • the equipment comprises a first gas inlet through which an inert gas is introduced into the equipment and which is connected to the additional oven.
  • the equipment also comprises a second gas inlet through which air or oxygen is introduced and which is connected to the commercial oven.
  • the equipment has a temperature controller in the first chamber of the additional oven, which is the element responsible for regulating the temperature ramps applied to the solid sample, and another temperature controller in the second chamber, which is responsible for regulating the temperature so that an appropriate heat transfer is produced, maintaining the temperature between the additional oven and the commercial oven and thus avoiding losses in the recording of the mercury signal.
  • the equipment allows mercury species to be identified in carbonaceous matrices without interferences resulting from the presence of organic matter with the signal collected in the mercury detector. It is also possible to evaluate the influence of different heating ramps on the sensitivity and selectivity of the desorption curves obtained for the pure mercury compounds.
  • the inclusion of the additional oven formed by two chambers makes easier to vary the number and type of applicable temperature ramps.
  • the desorption of mercury (i.e. is the release of the mercury species) takes place.
  • This additional oven is connected not only to the solid inlet for the sample, which is introduced inside a quartz boat, but also to the first gas inlet, through which an inert carrier gas is introduced, preferably Ar or N 2 , so the desorption takes place without any transformation.
  • an inert carrier gas preferably Ar or N 2
  • a control program that allows the generation of temperature curves between 25 and 700 °C is employed. Breaking down the mercury species at a controlled temperature allows each type of mercury to be correlated with its characteristic desorption temperature.
  • the mercury species When the mercury species is released from the solid without having undergone any transformation, it passes to the commercial oven, to which the second gas inlet (through which air or oxygen enters) is connected.
  • the temperature of the commercial oven is fixed at 800 °C.
  • the organic compounds of the sample are burned in the commercial oven and the oxidized mercury is reduced to Hg° which then passes to the mercury analyzer where it is measured. In the commercial oven, a total breakdown of the sample takes place for mercury determination.
  • the equipment of the invention contains an internal tube, preferably made of quartz, which passes through the additional oven and the commercial oven and connects them. In addition, this internal tube avoids corrosion and losses of mercury during the analysis.
  • Another technical problem to be solved is the control of the transfer of heat from the additional oven to the commercial oven since the heat transfer may not be homogeneous. This is solved by installing another temperature controller in the second chamber of the additional oven. This second temperature controller is connected to the first chamber of the additional oven and to the commercial oven to ensure that the heat transfer between them is controlled.
  • the second gas inlet through which oxygen or air is introduced, is located inside the quartz tube in the commercial oven to prevent the loss of mercury and to allow a proper quantitative analysis of the sample.
  • Another problem to be solved is to ensure that the equipment is versatile and allows an accurate, simple and quick analysis of the mercury species. More specifically to ensure a quick functioning of the equipment, a fan has been installed inside the additional oven to reduce the waiting time of the analysis from 5 hours to 3 hours.
  • the signal can be broken down into several, well differentiated peaks, improving the selectivity of the thermal desorption techniques while allowing more mercury species to be identified than would be possible identifiable with the state-of-the-art devices.
  • the equipment for identifying mercury species in solids of the present invention can be used to analyze any type of solid samples and in particular r the products and sub-products derived from the combustion and conversion of coal. Good results are also obtained when analyzing any type of fuel that contains carbonaceous material.
  • the ability to identify the mercury species present in the different solids of a thermal power plant makes it possible to predict mercury behavior during the process and to assess the risk of the residues and sub-products generated.
  • the equipment may also be used for analyzing any solid contaminated by mercury since the fate, the transport and the bioavailability of mercury are dependent on the species present.
  • Figure 1 shows a complete view of the equipment of the present invention.
  • Figure 2 shows a detailed view of the chambers and the ovens.
  • Figure 3a shows an example of the results obtained from identifying mercury species in a solid sample of coal with an state-of-the-art equipment.
  • Figure 3b shows an example of the results obtained from identifying mercury species in a solid sample of coal by means of the equipment of this invention.
  • the proposed equipment for identifying mercury species in solid samples uses the technique of thermal desorption.
  • the equipment comprises at least one solid inlet (1 ) for the solid sample, a commercially available oven (2) connected to a first temperature controller (3), a mercury analyzer (4) and a control unit (5).
  • the equipment also comprises an additional oven (6) which comprises a first chamber (7) and a second chamber (8) arranged one after the other.
  • This additional oven (6) is connected with the first chamber (7) to the solid inlet (1 ) for the solid sample and with the second chamber (8) to the commercial oven (2).
  • the additional oven allows the sample to be subjected to a wider range of temperatures resulting in a larger number and types of curves. This facilitates the correlation of the mercury species with the specific desorption temperature and enhances the accuracy of the results.
  • the equipment also comprises two gas inlets, namely a first gas inlet (9), through which an inert gas passes, and which is located in the additional oven (6) and a second gas inlet (10), through which air or oxygen passes, and which is located in the commercial oven (2).
  • the inert gas is used for the desorption of the mercury from the sample in the additional oven (6), avoiding possible interferences while oxygen is used to completely break down the sample in the commercial oven (2).
  • the equipment is also equipped two further temperature controllers, namely a second temperature controller (1 1 ) in the first chamber (7) of the additional oven (6) and a third temperature controller (12) in the second chamber (8) of the additional oven (6).
  • the equipment may comprise a gas station (13) with connections to the two gas inlets (9, 10) and with two gas flow controllers (14) for each connection to the gas inlets (9, 10).
  • the equipment has an internal tube (15) which passes through the additional oven (6) to the commercial oven (2) forming a continuous connection of the commercial oven (2) and the additional oven (6) to each other.
  • the internal tube (15) is preferably made of quartz which is a material that resists high temperatures.
  • the equipment can comprise an O-ring configured for sealing the joint between the additional oven and the commercial oven by way of the internal tube (15) which avoids the loss of mercury as it passes from the additional oven (6) to the commercial oven(2).
  • the equipment can comprise an O-ring configured for sealing the joint between the additional oven and the commercial oven by way of the internal tube (15) which avoids the loss of mercury as it passes from the additional oven (6) to the commercial oven(2).
  • thermocouple (16) In the solid inlet (1 ) for the solid sample, a sample holder with a thermocouple (16) is configured for continuously measuring the temperature of the sample.
  • Figures 3a and 3b show the results obtained from the identification of mercury species in a solid sample of coal using equipment of the state of the art (the result is shown in Figure 3a) and using the equipment of this invention (the result is shown in Figure 3b).
  • the data obtained with the equipment of the state of the art are less accurate and less selective.
  • the equipment of the state of the art has not allowed various mercury species to be identified due to the overlapping of signals in one single peak.
  • the equipment of the present invention has led to an increase in the accuracy and selectivity of the results, allowing different mercury species to be identified (shown in the graph in the form of two different temperature peaks).

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  • 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

Le dispositif d'analyse comprend une entrée (1) destinée à l'échantillon solide, un four commercial (2), un analyseur (4) et une unité de commande (5). Le dispositif d'analyse comprend également un four assemblé en laboratoire (four supplémentaire) (6) comprenant deux chambres, une première chambre (7) reliée à l'entrée (1) de solide destinée à l'échantillon solide et une seconde chambre (8) reliée au four commercial (2). L'équipement est doté d'une première entrée de gaz (9) destinée à un gaz inerte, qui est située dans le four supplémentaire (6), et d'une seconde entrée de gaz (10) destinée à de l'air ou de l'oxygène, située dans le four commercial (2). L'équipement comprend également trois dispositifs de régulation de température ; un premier dispositif de régulation de température (3) du four commercial (2), un deuxième dispositif de régulation de température de la première chambre (7) et un troisième dispositif de régulation de température de la seconde chambre (8). L'équipement permet d'analyser des échantillons solides.
PCT/EP2016/055198 2015-03-11 2016-03-10 Équipement d'identification d'espèce du mercure dans des solides Ceased WO2016142494A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES201530310A ES2582495B1 (es) 2015-03-11 2015-03-11 Equipo de identificación de especies de mercurio en sólidos
ESP201530310 2015-03-11

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WO2016142494A1 true WO2016142494A1 (fr) 2016-09-15

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ES (1) ES2582495B1 (fr)
WO (1) WO2016142494A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106442606A (zh) * 2016-09-28 2017-02-22 华中科技大学 一种识别汞形态的方法和装置
CN115144252A (zh) * 2022-07-13 2022-10-04 西南大学 一种高效富集树木年轮中痕量汞的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130236361A1 (en) * 2010-11-30 2013-09-12 Nippon Instruments Corporation Heating combustion tube, pyrolysis apparatus and mercury analyzing apparatus in analysis of mercury

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8133303B2 (en) * 2008-07-02 2012-03-13 Schwab James J Apparatus and method for controlling mercury pollution from a cement plant
WO2011020187A1 (fr) * 2009-08-19 2011-02-24 Mcgill University Procédés et systèmes pour la spéciation chimique quantitative de métaux lourds et d’autres polluants toxiques
CN202661381U (zh) * 2012-04-12 2013-01-09 中国科学院城市环境研究所 一种大气中不同形态汞样品的热脱附及分析装置
CN204122456U (zh) * 2014-10-14 2015-01-28 中节能大地环境修复有限公司 一种汞污染土壤热脱附处理装置

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130236361A1 (en) * 2010-11-30 2013-09-12 Nippon Instruments Corporation Heating combustion tube, pyrolysis apparatus and mercury analyzing apparatus in analysis of mercury

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
REIS A T ET AL: "Development and validation of a simple thermo-desorption technique for mercury speciation in soils and sediments", TALANTA, vol. 99, 7 June 2012 (2012-06-07), pages 363 - 368, XP028936838, ISSN: 0039-9140, DOI: 10.1016/J.TALANTA.2012.05.065 *
RUMAYOR M ET AL: "Application of thermal desorption for the identification of mercury species in solids derived from coal utilization", CHEMOSPHERE, PERGAMON PRESS, OXFORD, GB, vol. 119, 8 August 2014 (2014-08-08), pages 459 - 465, XP029109968, ISSN: 0045-6535, DOI: 10.1016/J.CHEMOSPHERE.2014.07.010 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106442606A (zh) * 2016-09-28 2017-02-22 华中科技大学 一种识别汞形态的方法和装置
CN106442606B (zh) * 2016-09-28 2019-01-15 华中科技大学 一种识别汞形态的方法和装置
CN115144252A (zh) * 2022-07-13 2022-10-04 西南大学 一种高效富集树木年轮中痕量汞的方法

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ES2582495B1 (es) 2017-06-21
ES2582495A1 (es) 2016-09-13

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