WO2001067092A2 - Continuous analyzer of volatile organic compounds, device and method for continuously assessing the quality of inside ambient air and use of said device for monitoring a ventilation installation - Google Patents

Continuous analyzer of volatile organic compounds, device and method for continuously assessing the quality of inside ambient air and use of said device for monitoring a ventilation installation Download PDF

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Publication number
WO2001067092A2
WO2001067092A2 PCT/FR2001/000695 FR0100695W WO0167092A2 WO 2001067092 A2 WO2001067092 A2 WO 2001067092A2 FR 0100695 W FR0100695 W FR 0100695W WO 0167092 A2 WO0167092 A2 WO 0167092A2
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Prior art keywords
sensor
air
sensors
channel
quality
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PCT/FR2001/000695
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French (fr)
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WO2001067092A3 (en
Inventor
Bernard Millancourt
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Electricite De France Service National
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Application filed by Electricite De France Service National filed Critical Electricite De France Service National
Priority to US10/220,104 priority Critical patent/US20030012696A1/en
Priority to CA002402371A priority patent/CA2402371A1/en
Priority to EP01913964A priority patent/EP1261867A2/en
Publication of WO2001067092A2 publication Critical patent/WO2001067092A2/en
Publication of WO2001067092A3 publication Critical patent/WO2001067092A3/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0011—Sample conditioning
    • G01N33/0014—Sample conditioning by eliminating a gas
    • 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
    • G01N33/0031—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array
    • G01N33/0032—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array using two or more different physical functioning modes
    • 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
    • G01N33/0047—Organic compounds
    • 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
    • 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
    • G01N33/0031—General constructional details of gas analysers, e.g. portable test equipment concerning the detector comprising two or more sensors, e.g. a sensor array
    • 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
    • G01N33/0047—Organic compounds
    • G01N33/0049—Halogenated organic compounds

Definitions

  • the present invention relates to a continuous volatile organic compound (VOC) analyzer, a device and a method for continuous assessment of the quality of indoor ambient air and a use of this device for controlling a ventilation installation. .
  • VOC volatile organic compound
  • H 2 0 The humidity and the water content by weight are recognized comfort factors. They are also indicators of human presence like C0, but much less precise taking into account the great variability of the natural humidity levels of the air, and the low emissions linked to the human presence compared to the high contents of the ambiant air.
  • C0 2 Carbon dioxide is not really considered a pollutant, but it is an excellent indicator of human presence in premises in the tertiary sector. It is also a good indicator of poor ventilation in residential premises, especially when using cooking or auxiliary heating appliances.
  • Carbon monoxide is a pollutant, the presence of which inside premises in the tertiary sector is essentially due to contributions of polluted outside air, to faulty combustion or to tobacco smoke. In residential premises he is responsible for a considerable number of fatal accidents each year due to defective combustion appliances, or those not connected to smoke exhaust pipes.
  • Nitrogen oxides can be represented by the dioxide N0 2 which is the most harmful and the only one concerned by the regulation in outside ambient air. In premises in the tertiary sector, the presence of NOx is mainly due to the supply of polluted outside air.
  • VOC Volatile Organic Compounds include a considerable number of compounds whose harmfulness is very variable. Among these, formaldehyde (HCHO) is chosen as an indicator; it is a product of degradation of materials, frequently emitted inside premises, irritating mucous membranes and whose long-term toxicity is now recognized. These various compounds can be used to establish an "index" of air quality. However, it is excluded, mainly for cost reasons, to use specific analyzers with high metrological performance. Indeed, a semi-quantitative determination with good reliability is acceptable.
  • HCHO formaldehyde
  • the invention therefore firstly relates to a continuous analyzer of volatile compounds. It also relates to a device and a method for continuous assessment of the quality of indoor ambient air, compact, simple to use and maintenance, of moderate cost, and capable of restoring an index of quality of air defined on the basis of pollutant contents and their relative harmfulness; allowing reliable and selective quantification of the five compounds defined above, in real time using commercial micro-sensors.
  • the present invention relates to a continuous analyzer of volatile organic compounds, characterized in that it comprises:
  • a measurement module comprising a first CO / VOC sensor and a second H 2 0 sensor
  • a sequential air treatment circuit comprising: • a filter,
  • a cartridge for the selective retention of volatile organic compounds placed on a first channel in parallel with a second direct channel, • a solenoid valve controlled by a sequencer, which switches the first channel - second channel,
  • a pump located downstream of the sensors so that the air to be analyzed is sucked through the filter and is transferred to the CO / COV and H 2 0 sensors either directly or after passing through the cartridge,
  • the present invention also relates to a device for continuous evaluation of the quality of the indoor ambient air comprising such a continuous analyzer of volatile compounds, in which the measurement module also includes the sensitive elements of sensors for NO 2 and CO 2 , and in which the circuit for sequential treatment of the air sucked by the pump through the dust filter first scans the third N0 sensor 2 and the fourth C0 sensor before being transferred to the first sensor of H 2 0 and the second CO / VOC sensor through the first or second channel.
  • the first, the second and the third sensors are chemical microsensors with metal oxides.
  • the pump is a diaphragm pump.
  • the present invention also relates to a method for continuously evaluating the quality of indoor ambient air using the above device, and which comprises the following steps:
  • a quality index is determined for each compound measured by referring to an evaluation grid which gives an index value for each compound as a function of different thresholds of content of compounds, referring to health data,
  • the above device can be advantageously used for controlling a ventilation installation.
  • FIG. 1 illustrates the device of one invention.
  • FIG. 2 illustrates the response curve of the sensor 20.
  • FIG. 3 illustrates the calibration curve of the sensor 16.
  • FIG. 4 illustrates a measurement sequence.
  • FIG. 5 illustrates the exploitation of the output signals from the sensors 15 and 16.
  • the continuous volatile organic compound analyzer 10 successively comprises:
  • a filter 11 which may be a coarse dust filter
  • a cartridge 12 for selective retention of volatile organic compounds placed on a channel 2 in parallel with a direct channel 1,
  • a pump 17 which can be a diaphragm pump
  • circuit 18 for processing the signals coming from the sensors 15 and 16 and from the sequencer 14.
  • the air to be analyzed is sucked by the pump 17 through the filter 11 and is transferred to the CO / COV sensors 15 and H 2 0 16, either directly or after passage through the cartridge 12; the sequential switching being ensured by the solenoid valve 13.
  • the pump 17 which ensures the sampling of the air, is placed downstream of the analysis circuit so as to avoid any contamination or retention of species.
  • the analyzer of the invention therefore has two main parts:
  • a measurement module which includes the sensitive elements of the CO / VOC and H0 sensors 15 and 16, the supply and measurement circuits and a sequential processing circuit for the sampled air,
  • a module 18 for processing and processing the signals.
  • the device for continuously evaluating the quality of the indoor ambient air includes all the elements of the analyzer 10 of the invention, as defined above. It further comprises a third N0 2 20 sensor, and a fourth C0 2 21 sensor disposed between the filter 11 and the channels 1 and 2.
  • the method for continuously evaluating the quality of indoor ambient air comprises the following steps:
  • a global index i g ⁇ 0ba i of the air quality is obtained as a function of the various composite indices thus obtained.
  • the sensors 15, 16 and 20 of CO / VOC, of H 2 O and of N 2 used are chemical microsensors with metal oxides available on the market.
  • a sensor of this type consists of a semiconductor sensitive element, most often based on tin oxide Sn0 2 , brought to its optimum operating temperature by a heating element, and whose electrical characteristics vary according to the presence in ambient air of gaseous compounds.
  • the sensitive element is the seat of absorption-desorption and oxidation-reduction phenomena whose equilibria are determined mainly by the temperature.
  • the electronics of such a sensor are very simple.
  • the C0 2 sensor 21 is an infrared (IR) sensor. Indeed, C0 2 has the property of absorbing infrared radiation with a maximum absorption between 4000 nm and 4400 nm. For a given geometry of the measuring cell, the absorption of the radiation is directly related to the C0 concentration (Beer-Lambert law). This sensor 21 could also be a chemical microsensor.
  • IR infrared
  • the sensitive elements of sensors 20 and 21 of NO 2 and CO can be placed on a support and be exposed directly to the ambient air sampled by means of the membrane pump.
  • the C0 sensor 21 is integral with its electronics and is used as intended by the supplier after having been removed from its protective casing for reasons of bulk.
  • the CO / COV and H 2 0 sensors 15 and 16 are placed under a cover allowing alternating scanning, either directly by ambient air, or after passage through the cartridge 12.
  • the cartridge 12 for the selective retention of volatile organic compounds can be produced using potassium permanganate.
  • the air flow rate to be purified must be low so as to ensure sufficient contact time for complete trapping, in practice, a flow rate of 0.3 1 / min and a 200 mm cartridge can be used. A lower flow makes it possible to reduce the size of the cartridge without affecting its autonomy.
  • the impregnation is very simply carried out by immersion of 100 g of alumina in an acidified aqueous solution (H 2 S0 4 10 ⁇ 2 N) containing 60 g / 1 of potassium permanganate. After spinning, the alumina beads are dried at 60-70 ° C for about 4 h and stored away from air, this treatment makes it possible to obtain an alumina containing 5% by mass of KMn0 4 .
  • 100 g of this preparation fill 6 cartridges of 200 mm / diameter 20 mm.
  • the pump 17 can be an ISA type diaphragm pump used in gas analyzers, separated from the sensors for reasons of space; but it can also be a smaller pump dimension that can be easily placed in the measuring box.
  • the duration of the cycle of the control signal of the solenoid valve 13, supplied by the sequencer 14, can be chosen between 30 seconds and three hours, for example 5 minutes.
  • the circuit 18 for processing the output signals delivered by the sensors 15, 16, 20, 21 is produced using a 70-channel AOIP acquisition center coupled to a PC type computer; the mathematical processing of the signals being carried out using software of the EXCEL type. It is also possible to use microprocessors integrated into the device of the invention.
  • the measurement is carried out by exposure of the N0 2 sensor 20 to the sampled air flow.
  • the senor 20 offers a response to nitrogen dioxide in a relatively narrow concentration range (0 to 200 ppb), but adapted to the levels encountered in the premises considered, with a fairly good selectivity which allows exploitation. direct signal.
  • the measurement of H 2 0 is carried out using the sensor 16 which offers good sensitivity and good selectivity to water; its response is linked to the water content by weight (expressed in mass / m 3 or in ppm), and not to the relative humidity of the air.
  • the response of this sensor 16, illustrated in FIG. 3, is used both for the measurement of the water content but also to correct the influence of the latter on the response to CO and to the VOCs of the sensor 15.
  • the CO, H 2 0 and VOC contents are measured using the two sensors 15 and 16.
  • VOC Volatile Organic Compounds
  • Total VOCs a few tens of ppb to 1 ppm.
  • the air sampled by the pump 17 is thus admitted to the two sensors 15 and 16, either directly or after passage through the cartridge 12 as illustrated in FIG. 4. 5-minute sequences are chosen.
  • the signal sampling phases are illustrated in FIG. 5 showing a typical evolution of the signals during a test.
  • the measurement is carried out using sensor 21.
  • This infrared sensor freed from its protective case, is integrated without modification of the device.
  • This sensor has good response linearity in its measurement range (0 to 2000 ppm), and good sensitivity.
  • the calibration curve is of the type:
  • [N0 2 ] aE (n) where: [N0 2 ] represents the concentration expressed in ppb E represents the sensor signal (in Volts).
  • the equation of the calibration curve of sensor 16 is of the type:
  • E 0 represents the base voltage of the sensor.
  • E 0 represents the base voltage of the sensor 15
  • E (H2 o) represents the correction of the influence of the water content on the sensor 15, from the content delivered by the sensor 16.
  • Formaldehyde and volatile organic compounds expressed in "formaldehyde equivalents" / sensor 15 "channel 1 - channel
  • the cartridge 12 quantitatively stops the following compounds and families of compounds: - formaldehyde and other aldehydes,
  • CO toxic
  • the CO measurement includes the possible presence of alkanes. In the presence of these compounds, the measurement is made by excess; this is an advantage by allowing the device to react to the presence of methane in the event of a natural gas leak, for example.
  • the influence of the variations in water content on the sensor 15 is very simply corrected by assigning the difference in the signals "channel 1-channel 2" measured on the sensor 16 by a coefficient S representing the ratio of the respective sensitivities to the water from these two sensors, i.e. the ratio of the slopes of the two response curves in a humidity range from 5000 to 25000 ppm.
  • the variations in water contents at the level of the sensor 15, downstream of the cartridge 12, are between 0 and + 6000 ppm; a fixed ratio of 1.67 is therefore retained between the raw voltages delivered by the sensors 15 and 16 for the same water content.
  • the value of 1.67 corresponding to the maximum difference in water content is preferably used at an average coefficient, because it allows a better adequacy of correction insofar as, only the large differences have a significant impact on the results.
  • VOC in mg / m 3 of HCHO
  • the difference "channel 1- channel 2" of the first term makes it possible to correct the response of this sensor to the CO not trapped by the cartridge 12 and to overcome possible zero drifts of the sensor 15 over time.
  • Calibration is carried out by injection and spraying of known quantities of HCHO in 37% aqueous solution; Table 2 at the end of the description provides the values of the signals after processing described above.
  • the calibration curve is a straight line in a concentration range between 0 and 6 mg / m 3 .
  • one solution consists in comparing the measured content of each of the selected compounds: H 2 0, CO, N0 2 , HCHO, C0 2 at different thresholds as in the grid in Table 3.
  • the concentration levels likely to be reached by each of these levels are divided into 10 classes established either from regulatory thresholds where they exist, or from recommendations of the World Health Organization for the protection of health and constitute each a basic clue.
  • the overall index is represented by the largest index of the elementary indices corresponding to each of the selected compounds.
  • CO index is as follows: Regulatory limit in the working environment: 50 ppm over an 8-hour period.
  • an index 10 corresponds to:

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Abstract

The invention concerns a continuous analyzer of volatile organic compounds (10) comprising a circuit (18) for sequential treatment of air such that air is sucked up by a pump (17) through a filter (11) and sweeps over a first sensor (15) for carbon monoxide and volatile organic compounds and a second sensor (16) for water vapour, either directly through a first path, or after passing in a cartridge (12) retaining organic species through a second path; switching from one of said paths to the other is provided by an electrically powered valve (13) controlled by a sequencer (14). The invention also concerns a device and a method for continuously assessing the quality of inside ambient air.

Description

ANALYSEUR EN CONTINU DE COMPOSES ORGANIQUES VOLATILS, CONTINUOUS ANALYZER OF VOLATILE ORGANIC COMPOUNDS,
DISPOSITIF ET PROCEDE D'EVALUATION EN CONTINU DE LADEVICE AND METHOD FOR CONTINUOUS EVALUATION OF THE
QUALITE DE L'AIR AMBIANT INTERIEUR ET UTILISATION DE CEINDOOR AMBIENT AIR QUALITY AND USE OF THE SAME
DISPOSITIF POUR LE PILOTAGE D'UNE INSTALLATION DE VENTILATIONDEVICE FOR CONTROLLING A VENTILATION SYSTEM
DESCRIPTIONDESCRIPTION
DOMAINE TECHNIQUETECHNICAL AREA
La présente invention concerne un analyseur en continu de composés organiques volatils (COV) , un dispositif et un procédé d'évaluation en continu de la qualité de l'air ambiant intérieur et une utilisation de ce dispositif pour le pilotage d'une installation de ventilation.The present invention relates to a continuous volatile organic compound (VOC) analyzer, a device and a method for continuous assessment of the quality of indoor ambient air and a use of this device for controlling a ventilation installation. .
ÉTAT DE LA TECHNIQUE ANTÉRIEUREPRIOR STATE OF THE ART
Différents paramètres sont susceptibles de caractériser la qualité de l'air ambiant intérieur, et notamment les teneurs en H20, C02 , CO, NOx et COV. Si l'on analyse successivement chacun de ces composés, on a : H20 : L'hygrométrie et la teneur pondérale en eau sont des facteurs de confort reconnus. Ce sont également des indicateurs de présence humaine comme le C0 , mais beaucoup moins précis compte tenu de la grande variabilité des taux d'humidité naturelle de l'air, et des faibles émissions liées à la présence humaine en regard des teneurs élevées de l'air ambiant. C02 : Le dioxyde de carbone n'est pas véritablement considéré comme un polluant, mais il est un excellent indicateur de présence humaine dans des locaux du secteur tertiaire. Il est également un bon indicateur de mauvaise ventilation dans des locaux d'habitation en particulier lors d'utilisation d'appareils de cuisson ou de chauffage d'appoint.Different parameters are likely to characterize the quality of the indoor ambient air, and in particular the H 2 0, C0 2 , CO, NOx and VOC contents. If we successively analyze each of these compounds, we have: H 2 0: The humidity and the water content by weight are recognized comfort factors. They are also indicators of human presence like C0, but much less precise taking into account the great variability of the natural humidity levels of the air, and the low emissions linked to the human presence compared to the high contents of the ambiant air. C0 2 : Carbon dioxide is not really considered a pollutant, but it is an excellent indicator of human presence in premises in the tertiary sector. It is also a good indicator of poor ventilation in residential premises, especially when using cooking or auxiliary heating appliances.
CO : Le monoxyde de carbone est un polluant dont la présence à 1 ' intérieur des locaux du secteur tertiaire est essentiellement due à des apports d'air extérieur pollué, à une combustion défectueuse ou encore à la fumée de tabac. Dans les locaux d'habitation il est responsable d'un nombre considérable d'accidents mortels chaque année à cause d'appareillage de combustion défectueux, ou non raccordés à des conduits d'évacuation de fumée.CO: Carbon monoxide is a pollutant, the presence of which inside premises in the tertiary sector is essentially due to contributions of polluted outside air, to faulty combustion or to tobacco smoke. In residential premises he is responsible for a considerable number of fatal accidents each year due to defective combustion appliances, or those not connected to smoke exhaust pipes.
NOx : Les oxydes d'azote peuvent être représentés par le dioxyde N02 qui est le plus nocif et le seul concerné par la réglementation en air ambiant extérieur. Dans les locaux du secteur tertiaire, la présence des NOx est essentiellement due à des apports d'air extérieur pollué.NOx: Nitrogen oxides can be represented by the dioxide N0 2 which is the most harmful and the only one concerned by the regulation in outside ambient air. In premises in the tertiary sector, the presence of NOx is mainly due to the supply of polluted outside air.
COV : Les Composés Organiques Volatils regroupent un nombre considérable de composés dont la nocivité est très variable. Parmi ceux-ci, le formaldéhyde (HCHO) est choisi comme indicateur ; c'est un produit de dégradation des matériaux, fréquemment émis à l'intérieur de locaux, irritant des muqueuses et dont la toxicité à long terme est maintenant reconnue. Ces différents composés peuvent être utilisés pour établir un "indice" de qualité d'air. Or il est exclu, principalement pour des raisons de coût, d'utiliser des analyseurs spécifiques à hautes performances métrologiques . En effet, une détermination semi-quantitative avec une bonne fiabilité est acceptable.VOC: Volatile Organic Compounds include a considerable number of compounds whose harmfulness is very variable. Among these, formaldehyde (HCHO) is chosen as an indicator; it is a product of degradation of materials, frequently emitted inside premises, irritating mucous membranes and whose long-term toxicity is now recognized. These various compounds can be used to establish an "index" of air quality. However, it is excluded, mainly for cost reasons, to use specific analyzers with high metrological performance. Indeed, a semi-quantitative determination with good reliability is acceptable.
L'invention a donc tout d'abord pour objet un analyseur en continu de composés volatils . Elle a également pour objet un dispositif et un procédé d'évaluation en continu de la qualité de l'air ambiant intérieur, peu encombrant, simple d'utilisation et de maintenance, de coût modéré, et capable de restituer un indice de qualité d'air défini à partir des teneurs en polluants et de leurs nocivités relatives ; permettant de quantifier de manière fiable et sélective les cinq composés définis ci-dessus, en temps réel à l'aide de micro-capteurs du commerce.The invention therefore firstly relates to a continuous analyzer of volatile compounds. It also relates to a device and a method for continuous assessment of the quality of indoor ambient air, compact, simple to use and maintenance, of moderate cost, and capable of restoring an index of quality of air defined on the basis of pollutant contents and their relative harmfulness; allowing reliable and selective quantification of the five compounds defined above, in real time using commercial micro-sensors.
EXPOSÉ DE L'INVENTIONSTATEMENT OF THE INVENTION
La présente invention concerne un analyseur en continu de composés organiques volatils, caractérisé en ce qu'il comprend :The present invention relates to a continuous analyzer of volatile organic compounds, characterized in that it comprises:
- un module de mesure comportant un premier capteur de CO/COV et un second capteur de H20,- a measurement module comprising a first CO / VOC sensor and a second H 2 0 sensor,
- un circuit de traitement séquentiel de 1 ' air comportant : • un filtre,- a sequential air treatment circuit comprising: • a filter,
• une cartouche de rétention sélective des composés organiques volatils disposée sur une première voie en parallèle avec une seconde voie directe, • une électrovanne commandée par un sequenceur, qui assure la commutation première voie - seconde voie,A cartridge for the selective retention of volatile organic compounds placed on a first channel in parallel with a second direct channel, • a solenoid valve controlled by a sequencer, which switches the first channel - second channel,
• une pompe située en aval des capteurs de manière à ce que 1 ' air à analyser soit aspiré à travers le filtre et soit transféré vers les capteurs CO/COV et H20 soit directement, soit après passage à travers la cartouche,A pump located downstream of the sensors so that the air to be analyzed is sucked through the filter and is transferred to the CO / COV and H 2 0 sensors either directly or after passing through the cartridge,
- un circuit de traitement des signaux provenant des capteurs et du sequenceur, permettant d'accéder aux trois paramètres suivants :- a signal processing circuit from the sensors and the sequencer, allowing access to the following three parameters:
- la teneur en eau de l'air,- the water content of the air,
- la teneur en CO de l'air sur un échantillon débarrassé des COV, - la teneur en COV, en opérant une différence de signaux obtenus grâce au capteur de CO/COV lorsque l'air à analyser est transféré vers celui-ci soit au travers de la première voie soit au travers de la seconde voie. La présente invention concerne également un dispositif d'évaluation en continu de la qualité de 1 ' air ambiant intérieur comprenant un tel analyseur en continu de composés volatils, dans lequel le module de mesure comporte également les éléments sensibles de capteurs de N02 et de C02 , et dans lequel le circuit de traitement séquentiel de l'air aspiré par la pompe à travers le filtre à poussière balaye tout d'abord le troisième capteur de N02 et le quatrième capteur de C0 avant d'être transféré vers le premier capteur de H20 et le second capteur de CO/COV au travers de la première ou de la deuxième voie. Avantageusement le premier, le second et le troisième capteurs sont des microcapteurs chimiques à oxydes métalliques. La pompe est une pompe à membrane.- the CO content of the air on a sample free of VOCs, - the VOC content, by operating a difference in signals obtained thanks to the CO / VOC sensor when the air to be analyzed is transferred to it either at across the first lane or across the second lane. The present invention also relates to a device for continuous evaluation of the quality of the indoor ambient air comprising such a continuous analyzer of volatile compounds, in which the measurement module also includes the sensitive elements of sensors for NO 2 and CO 2 , and in which the circuit for sequential treatment of the air sucked by the pump through the dust filter first scans the third N0 sensor 2 and the fourth C0 sensor before being transferred to the first sensor of H 2 0 and the second CO / VOC sensor through the first or second channel. Advantageously, the first, the second and the third sensors are chemical microsensors with metal oxides. The pump is a diaphragm pump.
La présente invention concerne également un procédé d'évaluation en continu de la qualité de l'air ambiant intérieur mettant en œuvre le dispositif ci- dessus, et qui comporte les étapes suivantes :The present invention also relates to a method for continuously evaluating the quality of indoor ambient air using the above device, and which comprises the following steps:
- on détermine la courbe de calibrage de chacun des capteurs de mesure des différents composés : H20, CO/COV, N02 et C02,- the calibration curve of each of the sensors for measuring the different compounds is determined: H 2 0, CO / COV, N0 2 and C0 2 ,
- on corrige par calcul 1 ' influence des composés interférants majoritaires,- the influence of the majority interfering compounds is corrected by calculation,
- on transpose le signal de sortie de chaque capteur en teneur de composé mesuré, en tenant compte de sa courbe de calibrage,- the output signal of each sensor is transposed into the content of the measured compound, taking into account its calibration curve,
- on détermine un indice de qualité pour chaque composé mesuré en faisant référence à une grille d'évaluation qui donne une valeur d'indice pour chaque composé en fonction de différents seuils de teneurs de composés, se référant à des données sanitaires,a quality index is determined for each compound measured by referring to an evaluation grid which gives an index value for each compound as a function of different thresholds of content of compounds, referring to health data,
- on obtient un indice global de la qualité de l'air en fonction des différents indices composés obtenus .- an overall index of air quality is obtained as a function of the various composite indices obtained.
Le dispositif précédent peut être avantageusement utilisé pour le pilotage d'une installation de ventilation.The above device can be advantageously used for controlling a ventilation installation.
BRÈVE DESCRIPTION DES DESSINSBRIEF DESCRIPTION OF THE DRAWINGS
La figure 1 illustre le dispositif de 1 ' invention. La figure 2 illustre la courbe de réponse du capteur 20.Figure 1 illustrates the device of one invention. FIG. 2 illustrates the response curve of the sensor 20.
La figure 3 illustre la courbe de calibrage du capteur 16. La figure 4 illustre une séquence de mesure .FIG. 3 illustrates the calibration curve of the sensor 16. FIG. 4 illustrates a measurement sequence.
La figure 5 illustre l'exploitation des signaux de sortie des capteurs 15 et 16.FIG. 5 illustrates the exploitation of the output signals from the sensors 15 and 16.
EXPOSÉ DÉTAILLÉ DE MODES DE RÉALISATION PARTICULIERSDETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
Comme illustré sur la figure 1, l'analyseur en continu de Composés Organiques Volatils 10 comprend successivement :As illustrated in FIG. 1, the continuous volatile organic compound analyzer 10 successively comprises:
- un filtre 11, qui peut être un filtre à poussières grossier, - une cartouche 12 de rétention sélective des composés organiques volatils disposée sur une voie 2 en parallèle avec une voie 1 directe,a filter 11, which may be a coarse dust filter, a cartridge 12 for selective retention of volatile organic compounds placed on a channel 2 in parallel with a direct channel 1,
- une électrovanne 13 commandée par un sequenceur 14, qui assure la commutation voie 1-voie 2, - un premier capteur de CO/COV 15 et un second capteur de H0 16,- a solenoid valve 13 controlled by a sequencer 14, which switches channel 1-channel 2, - a first CO / COV sensor 15 and a second H0 sensor 16,
- une pompe 17 qui peut être une pompe à membrane ,a pump 17 which can be a diaphragm pump,
- un circuit 18 de traitement des signaux provenant des capteurs 15 et 16 et du sequenceur 14.a circuit 18 for processing the signals coming from the sensors 15 and 16 and from the sequencer 14.
L'air à analyser est aspiré par la pompe 17 à travers le filtre 11 et est transféré vers les capteurs CO/COV 15 et H20 16, soit directement, soit après passage à travers la cartouche 12 ; la commutation séquentielle étant assurée par 1 ' électrovanne 13.The air to be analyzed is sucked by the pump 17 through the filter 11 and is transferred to the CO / COV sensors 15 and H 2 0 16, either directly or after passage through the cartridge 12; the sequential switching being ensured by the solenoid valve 13.
La pompe 17, qui permet d'assurer l'échantillonnage de l'air, est placée en aval du circuit d'analyse de manière à éviter toute contamination ou rétention d'espèces.The pump 17, which ensures the sampling of the air, is placed downstream of the analysis circuit so as to avoid any contamination or retention of species.
L'analyseur de l'invention comporte donc deux parties principales :The analyzer of the invention therefore has two main parts:
- un module de mesure, qui comporte les éléments sensibles des capteurs 15 et 16 de CO/COV et de H0, les circuits d'alimentation et de mesure et un circuit de traitement séquentiel de l'air échantillonné,- a measurement module, which includes the sensitive elements of the CO / VOC and H0 sensors 15 and 16, the supply and measurement circuits and a sequential processing circuit for the sampled air,
- un module 18 de traitement et d'exploitation des signaux.a module 18 for processing and processing the signals.
Le dispositif d'évaluation en continu de la qualité de l'air ambiant intérieur selon l'invention, illustré sur la figure 1, comprend tous les éléments de l'analyseur 10 de l'invention, tels que définis ci- dessus. Il comprend de plus un troisième capteur de N02 20, et un quatrième capteur de C02 21 disposés entre le filtre 11 et les voies 1 et 2.The device for continuously evaluating the quality of the indoor ambient air according to the invention, illustrated in FIG. 1, includes all the elements of the analyzer 10 of the invention, as defined above. It further comprises a third N0 2 20 sensor, and a fourth C0 2 21 sensor disposed between the filter 11 and the channels 1 and 2.
Le procédé d'évaluation en continu de la qualité de l'air ambiant intérieur selon l'invention, mettant en œuvre le dispositif défini ci-dessus, comporte les étapes suivantes :The method for continuously evaluating the quality of indoor ambient air according to the invention, implementing the device defined above, comprises the following steps:
- on détermine la courbe de calibrage de chacun des capteurs 15, 16, 20 et 21 de mesure des différents composés : H20, CO/COV, N02 et C0 , - on corrige par calcul l'influence des composés interférants majoritaires, - on transpose le signal de sortie de chaque capteur en teneur de composé mesuré, en tenant compte de sa courbe de calibrage et des interférants majoritaires, - on détermine un indice de qualité pour chaque composé mesuré en faisant référence à une grille d'évaluation, comme celle illustrée à titre d'exemple dans le tableau 3, qui donne une valeur d'indice pour chaque composé en fonction de différents seuils de teneurs de composés se référant à des données sanitaires ,- the calibration curve of each of the sensors 15, 16, 20 and 21 for measuring the various compounds is determined: H 2 0, CO / COV, N0 2 and C0, - the influence of the majority of interfering compounds is corrected by calculation, - the output signal of each sensor is transposed into the content of the measured compound, taking into account its calibration curve and the majority of interferants, - a quality index is determined for each compound measured by reference to an evaluation grid, like that illustrated by way of example in Table 3, which gives an index value for each compound as a function of different thresholds of content of compounds referring to health data,
- on obtient un indice global igι0bai de la qualité de l'air en fonction des différents indices composés ainsi obtenus.- A global index i g ι 0ba i of the air quality is obtained as a function of the various composite indices thus obtained.
EXEMPLE DE REALISATIONEXAMPLE OF IMPLEMENTATION
Dans un exemple de réalisation, les capteurs 15, 16 et 20 de CO/COV, de H20 et de N02 utilisés sont des microcapteurs chimiques à oxydes métalliques disponibles dans le commerce. Un capteur de ce type est constitué d'un élément sensible semiconducteur, le plus souvent à base d'oxyde d'étain Sn02 , porté à sa température optimale de fonctionnement grâce à un élément chauffant, et dont les caractéristiques électriques varient en fonction de la présence dans l'air ambiant de composés gazeux. L'élément sensible est le siège de phénomènes d ' absorption-désorption et d ' oxydo-réduction dont les équilibres sont déterminés principalement par la température. L'électronique d'un tel capteur est très simple .In an exemplary embodiment, the sensors 15, 16 and 20 of CO / VOC, of H 2 O and of N 2 used are chemical microsensors with metal oxides available on the market. A sensor of this type consists of a semiconductor sensitive element, most often based on tin oxide Sn0 2 , brought to its optimum operating temperature by a heating element, and whose electrical characteristics vary according to the presence in ambient air of gaseous compounds. The sensitive element is the seat of absorption-desorption and oxidation-reduction phenomena whose equilibria are determined mainly by the temperature. The electronics of such a sensor are very simple.
Le capteur 21 de C02 est un capteur infrarouge (IR) . En effet, le C02 a la propriété d'absorber le rayonnement infrarouge avec un maximum d'absorption entre 4000 nm et 4400 nm. Pour une géométrie donnée de cellule de mesure, l'absorption du rayonnement est directement reliée à la concentration en C0 (loi de Beer-Lambert ) . Ce capteur 21 pourrait également être un microcapteur chimique.The C0 2 sensor 21 is an infrared (IR) sensor. Indeed, C0 2 has the property of absorbing infrared radiation with a maximum absorption between 4000 nm and 4400 nm. For a given geometry of the measuring cell, the absorption of the radiation is directly related to the C0 concentration (Beer-Lambert law). This sensor 21 could also be a chemical microsensor.
Parmi les différents types de capteurs possibles, on a retenu, à titre d'exemple les capteurs 15, 16, 20, 21 suivants :Among the different types of possible sensors, the following sensors 15, 16, 20, 21 have been chosen:
CO/COV : capteur FIGARO TGS 2620 H20 : capteur FIGARO TGS 2180 N02 : capteur FIGARO TGS 2105 C02 : capteur IR SAUTER/type EGQ220F001CO / COV: FIGARO TGS 2620 H 2 0 sensor: FIGARO TGS 2180 N0 2 sensor: FIGARO TGS 2105 C0 2 sensor: IR SAUTER sensor / type EGQ220F001
Les éléments sensibles des capteurs 20 et 21 de N02 et de C0 peuvent être disposés sur un support et être exposés directement à l'air ambiant échantillonné grâce à la pompe à membrane.The sensitive elements of sensors 20 and 21 of NO 2 and CO can be placed on a support and be exposed directly to the ambient air sampled by means of the membrane pump.
Le capteur 21 de C0 est solidaire de son électronique et est utilisé tel que prévu par le fournisseur après avoir été débarrassé de son boîtier protecteur pour des raisons d'encombrement.The C0 sensor 21 is integral with its electronics and is used as intended by the supplier after having been removed from its protective casing for reasons of bulk.
Les capteurs 15 et 16 de CO/COV et de H20 sont disposés sous un capot permettant un balayage en alternance, soit directement par l'air ambiant, soit après passage à travers la cartouche 12. La cartouche 12 de rétention sélective des composés organiques volatils peut être réalisée en utilisant du permanganate de potassium.The CO / COV and H 2 0 sensors 15 and 16 are placed under a cover allowing alternating scanning, either directly by ambient air, or after passage through the cartridge 12. The cartridge 12 for the selective retention of volatile organic compounds can be produced using potassium permanganate.
Les aldéhydes, cétones, alcools, en effet, réagissent avec le permanganate de potassium et sont arrêtés, par oxydation, d'une manière quantitative ; les composés benzéniques sont retenus, a priori, par adsorption ; Le débit d'air à épurer doit être faible de manière à assurer un temps de contact suffisant pour un piégeage complet, dans la pratique, un débit de 0,3 1/min et une cartouche de 200 mm sont utilisables. Un débit inférieur permet de réduire la dimension de la cartouche sans affecter son autonomie. De l'oxyde d'aluminium activé (alumine Al20 ) en billes microporeuses de 2 mm à 5 mm de diamètre, est utilisé comme support du composé actif constitué de permanganate de potassium (KMn04) . Pour obtenir une préparation pour 100 g, on réalise très simplement l'imprégnation par immersion de 100 g d'alumine dans une solution aqueuse acidifiée (H2S04 10~2N) à 60 g/1 de permanganate de potassium. Après essorage, les billes d'alumine sont séchées à 60-70°C pendant 4 h environ et conservées à l'abri de l'air, ce traitement permet d'obtenir une alumine renfermant 5% en masse de KMn04. 100 g de cette préparation permettent de remplir 6 cartouches de 200 mm/diamètre 20 mm.Aldehydes, ketones, alcohols, in fact, react with potassium permanganate and are stopped, by oxidation, in a quantitative way; the benzene compounds are retained, a priori, by adsorption; The air flow rate to be purified must be low so as to ensure sufficient contact time for complete trapping, in practice, a flow rate of 0.3 1 / min and a 200 mm cartridge can be used. A lower flow makes it possible to reduce the size of the cartridge without affecting its autonomy. Activated aluminum oxide (alumina Al 2 0) in microporous beads from 2 mm to 5 mm in diameter, is used as support for the active compound consisting of potassium permanganate (KMn0 4 ). To obtain a preparation for 100 g, the impregnation is very simply carried out by immersion of 100 g of alumina in an acidified aqueous solution (H 2 S0 4 10 ~ 2 N) containing 60 g / 1 of potassium permanganate. After spinning, the alumina beads are dried at 60-70 ° C for about 4 h and stored away from air, this treatment makes it possible to obtain an alumina containing 5% by mass of KMn0 4 . 100 g of this preparation fill 6 cartridges of 200 mm / diameter 20 mm.
La pompe 17 peut être une pompe à membrane de type ISA utilisée dans des analyseurs de gaz, séparée des capteurs pour des raisons d'encombrement ; mais ce peut également être une pompe de plus petite dimension pouvant être aisément disposée dans le boîtier de mesure.The pump 17 can be an ISA type diaphragm pump used in gas analyzers, separated from the sensors for reasons of space; but it can also be a smaller pump dimension that can be easily placed in the measuring box.
La durée du cycle du signal de commande de 1 ' électrovanne 13, fourni par le sequenceur 14, peut être choisie entre 30 secondes et trois heures, par exemple 5 minutes .The duration of the cycle of the control signal of the solenoid valve 13, supplied by the sequencer 14, can be chosen between 30 seconds and three hours, for example 5 minutes.
Le circuit 18 de traitement des signaux de sortie délivrés par les capteurs 15, 16, 20, 21 est réalisé à l'aide d'une centrale d'acquisition AOIP 70 voies couplées à un ordinateur de type PC ; le traitement mathématique des signaux étant effectué à l'aide d'un logiciel de type EXCEL. Il est également possible d'utiliser des microprocesseurs intégrés au dispositif de l'invention.The circuit 18 for processing the output signals delivered by the sensors 15, 16, 20, 21 is produced using a 70-channel AOIP acquisition center coupled to a PC type computer; the mathematical processing of the signals being carried out using software of the EXCEL type. It is also possible to use microprocessors integrated into the device of the invention.
Dans cet exemple de réalisation, on a effectué les mesures suivantes.In this exemplary embodiment, the following measurements were made.
Mesure du dioxyde d'azote (N0 )Nitrogen dioxide (N0) measurement
La mesure est effectuée par exposition du capteur 20 de N02 au flux d'air échantillonné.The measurement is carried out by exposure of the N0 2 sensor 20 to the sampled air flow.
Comme illustré sur la figure 2 le capteur 20 offre une réponse au dioxyde d'azote dans un domaine de concentration relativement étroit (0 à 200 ppb) , mais adapté aux niveaux rencontrés dans les locaux considérés, avec une assez bonne sélectivité qui permet une exploitation directe du signal.As illustrated in FIG. 2, the sensor 20 offers a response to nitrogen dioxide in a relatively narrow concentration range (0 to 200 ppb), but adapted to the levels encountered in the premises considered, with a fairly good selectivity which allows exploitation. direct signal.
L'incidence du CO sur la mesure du N0 , effective pour des rapports de concentrations C0/N0 élevés (supérieurs à 100) , a pu être négligée sans induire d'erreurs importantes.The effect of CO on the N0 measurement, effective for C0 / N0 concentration ratios high (greater than 100), could have been neglected without causing significant errors.
Mesure de l'humidité (H20)Humidity measurement (H 2 0)
La mesure de H20 est effectuée grâce au capteur 16 qui offre une bonne sensibilité et une bonne sélectivité à l'eau ; sa réponse est liée à la teneur pondérale en eau (exprimée en masse/m3 ou en ppm) , et non à l'humidité relative de l'air.The measurement of H 2 0 is carried out using the sensor 16 which offers good sensitivity and good selectivity to water; its response is linked to the water content by weight (expressed in mass / m 3 or in ppm), and not to the relative humidity of the air.
Le CO, le C02 , les NOx et les COV sont sans influence sur la mesure dans les domaines concernés par l'air ambiant.CO, C0 2 , NOx and VOCs have no influence on the measurement in the areas affected by the ambient air.
La réponse de ce capteur 16, illustrée sur la figure 3, est utilisée à la fois pour la mesure de la teneur en eau mais également pour corriger l'influence de cette dernière sur la réponse au CO et aux COV du capteur 15.The response of this sensor 16, illustrated in FIG. 3, is used both for the measurement of the water content but also to correct the influence of the latter on the response to CO and to the VOCs of the sensor 15.
Mesures associées du CO, de H20 et des COVAssociated CO, H 2 0 and VOC measurements
Les teneurs en CO, H20 et COV sont mesurées à l'aide des deux capteurs 15 et 16.The CO, H 2 0 and VOC contents are measured using the two sensors 15 and 16.
L ' évaluation des teneurs en CO et en Composés Organiques Volatils (COV) est effectuée à l'aide du capteur 15 multipolluants qui offre une bonne sensibilité aux COV mais nécessite une correction de l'influence de la teneur en eau effectuée grâce au second capteur 16 spécifique de l'eau. A l'intérieur des locaux, les COV sont présents à de très faibles concentrations en regard des teneurs en composés potentiellement interférants tels que CO ou H20 qui rendent très aléatoires les corrections par voie purement mathématique. Cette difficulté est contournée en réalisant un piegeage sélectif des COV à l'aide de la cartouche 12, en amont du capteur 15, et en admettant en alternance sur ce capteur 15 de l'air épuré et de l'air à analyser. Les interférants majeurs ne sont pas arrêtés et la différence des signaux permet d'accéder avec une bonne sensibilité à la teneur en COV.The evaluation of the CO and Volatile Organic Compounds (VOC) contents is carried out using the multi-pollutant sensor 15 which offers good sensitivity to VOCs but requires a correction of the influence of the water content carried out thanks to the second sensor 16 specific water. Inside the premises, VOCs are present at very low concentrations compared to contents of potentially interfering compounds such as CO or H 2 0 which make corrections very purely mathematically random. This difficulty is overcome by carrying out a selective trapping of the VOCs using the cartridge 12, upstream of the sensor 15, and by admitting alternately on this sensor 15 purified air and the air to be analyzed. Major interferants are not stopped and the difference in signals allows access with good sensitivity to the VOC content.
Les domaines concernés sont les suivants : H20 : 5000 à 25000 ppmThe areas concerned are as follows: H 2 0: 5,000 to 25,000 ppm
CO : 0 à 25 ppmCO: 0 to 25 ppm
COV totaux : quelques dizaines de ppb à 1 ppm. En opérant par différences calculées sur les signaux stabilisés au cours de chaque séquence, il est possible d'accéder à la concentration du composé masqué tout en s ' affranchissant des teneurs en composés interférants ainsi que des dérives de zéro du capteur. Les deux capteurs associés 15 et 16 permettent donc, selon la période d'échantillonnage du signal, d'accéder aux trois paramètres suivants avec une bonne précision :Total VOCs: a few tens of ppb to 1 ppm. By operating by calculated differences on the signals stabilized during each sequence, it is possible to access the concentration of the masked compound while being freed from the levels of interfering compounds as well as zero drift from the sensor. The two associated sensors 15 and 16 therefore make it possible, depending on the signal sampling period, to access the following three parameters with good accuracy:
- la teneur en eau de l'air ambiant, - la teneur en CO de l'air ambiant sur un échantillon débarrassé des COV,- the water content of the ambient air, - the CO content of the ambient air on a sample free of VOCs,
- la teneur en COV, en opérant par différence des signaux.- the VOC content, operating by difference of the signals.
L'air échantillonné grâce à la pompe 17 est ainsi admis sur les deux capteurs 15 et 16, soit directement, soit après passage au travers la cartouche 12 comme illustré sur la figure 4. Des séquences de 5 minutes sont choisies.The air sampled by the pump 17 is thus admitted to the two sensors 15 and 16, either directly or after passage through the cartridge 12 as illustrated in FIG. 4. 5-minute sequences are chosen.
Les signaux bruts délivrés par ces capteurs 15 et 16 sont échantillonnés après stabilisation, de la manière suivante : voie 1 (air ambiant) ==> capteur 16 = mesure de H20 ambiant, voie 2 (cartouche) => capteur 15 => mesure de CO ambiant (débarrassé des COV piégés) (voie 1-voie 2) = mesure des COV piégés.The raw signals delivered by these sensors 15 and 16 are sampled after stabilization, as follows: channel 1 (ambient air) ==> sensor 16 = measurement of ambient H 2 0, channel 2 (cartridge) => sensor 15 => ambient CO measurement (free of trapped VOCs) (channel 1-channel 2) = measurement of trapped VOCs.
Les phases d'échantillonnage des signaux sont illustrées par la figure 5 présentant une évolution typique des signaux au cours d'un essai.The signal sampling phases are illustrated in FIG. 5 showing a typical evolution of the signals during a test.
Mesure du C02 C0 2 measurement
La mesure est effectuée à l'aide du capteur 21. Ce capteur infrarouge, débarrassé de son boîtier de protection, est intégré sans modification du dispositif. Ce capteur présente une bonne linéarité de réponse dans sa gamme de mesure (0 à 2000 ppm) , et une bonne sensibilité.The measurement is carried out using sensor 21. This infrared sensor, freed from its protective case, is integrated without modification of the device. This sensor has good response linearity in its measurement range (0 to 2000 ppm), and good sensitivity.
Pour effectuer le traitement des signaux de sortie des capteurs, on considère les courbes de calibrage suivantes :To process the sensor output signals, consider the following calibration curves:
Dioxyde d'azote (N02) /capteur 20Nitrogen dioxide (N0 2 ) / sensor 20
La courbe de calibrage est du type :The calibration curve is of the type:
[N02] = aE(n) où : [N02] représente la concentration exprimée en ppb E représente le signal du capteur (en Volts) .[N0 2 ] = aE (n) where: [N0 2 ] represents the concentration expressed in ppb E represents the sensor signal (in Volts).
Teneur pondérale en eau (H20) /capteur 16 "voie 1"Water content by weight (H 2 0) / 16 "channel 1" sensor
L'équation de la courbe de calibrage du capteur 16 est du type :The equation of the calibration curve of sensor 16 is of the type:
HOen ppm = b . ( E-E0 ) 2+c . (E-E0 ) +d où : E représente la tension brute délivrée par le capteur (en Volts) etHO in pp m = b. (EE 0 ) 2 + c. (EE 0 ) + d where: E represents the raw voltage delivered by the sensor (in Volts) and
E0 représente la tension de base du capteur.E 0 represents the base voltage of the sensor.
Monoxyde de carbone (CO) /capteur 15 "voie 2"Carbon monoxide (CO) / 15 "channel 2" sensor
L'équation de la courbe de calibrage du capteur 15 vis-à-vis du CO est un polynôme du second degré du type :The equation of the calibration curve of the sensor 15 with respect to CO is a second degree polynomial of the type:
COen
Figure imgf000017_0001
• [E-Eo-E(H2o) ] +f - [E-E0-E(H2o) ] +9 où E représente la tension brute délivrée par le capteur 2620 (en Volts) ,CO in
Figure imgf000017_0001
• [E-Eo-E ( H2 o)] + f - [EE 0 -E (H2 o)] +9 where E represents the raw voltage delivered by the sensor 2620 (in Volts),
E0 représente la tension de base du capteur 15, E(H2o) représente la correction de l'influence de la teneur en eau sur le capteur 15, à partir de la teneur délivrée par le capteur 16.E 0 represents the base voltage of the sensor 15, E (H2 o) represents the correction of the influence of the water content on the sensor 15, from the content delivered by the sensor 16.
Formaldehyde et composés organiques volatils exprimés en "équivalents formaldehyde" /capteur 15 "voie 1 - voieFormaldehyde and volatile organic compounds expressed in "formaldehyde equivalents" / sensor 15 "channel 1 - channel
____________
Parmi les COV majeurs de l'air ambiant pollué, la cartouche 12 arrête quantitativement les composés et familles de composés suivants : - formaldehyde et autres aldéhydes,Among the major VOCs of polluted ambient air, the cartridge 12 quantitatively stops the following compounds and families of compounds: - formaldehyde and other aldehydes,
- cétones (acétone... ) ,- ketones (acetone ...),
- alcools (méthanol, éthanol...),- alcohols (methanol, ethanol ...),
- composés benzéniques. Tous ces composés ont une toxicité reconnue et le capteur 15 leur présente des sensibilités comparables. Parmi ces polluants, le formaldehyde s'avère majoritaire à l'intérieur des locaux et c'est l'ensemble de ces COV "indésirables" qui est exprimé en "équivalents formaldehyde" .- benzene compounds. All of these compounds have recognized toxicity and the sensor 15 presents them with comparable sensitivities. Among these pollutants, formaldehyde appears to be the majority inside the premises and it is all of these "undesirable" VOCs that are expressed in "formaldehyde equivalents".
Le CO (et les alcanes) présent dans l'air à des teneurs qui peuvent atteindre plusieurs ppm, n'est pas arrêté par la cartouche 12.The CO (and the alkanes) present in the air at levels which can reach several ppm, is not stopped by the cartridge 12.
Le CO, toxique, est mesuré lors de la séquence correspondant à la voie 2. La mesure du CO intègre la présence éventuelle d' alcanes. En cas de présence de ces composés, la mesure se fait par excès ; ceci constitue un atout en permettant au dispositif de réagir à la présence de méthane en cas de fuite de gaz naturel par exemple.CO, toxic, is measured during the sequence corresponding to channel 2. The CO measurement includes the possible presence of alkanes. In the presence of these compounds, the measurement is made by excess; this is an advantage by allowing the device to react to the presence of methane in the event of a natural gas leak, for example.
Pour chaque palier de réponse, les moyennes en voie 1 et en voie 2 sont calculées en éliminant les phases de stabilisation (1 minute environ avant et après chaque commutation) . • Pour le capteur 15 on a :For each response level, the averages on channel 1 and channel 2 are calculated by eliminating the stabilization phases (approximately 1 minute before and after each switching). • For sensor 15 we have:
- Voie 2 (piegeage) : 0,5 x [moyenne (tO+7 à tO+9 ) +moyenne ( t0+17 à tO+19)] (moyenne des signaux des séquences "voie 2" précédant et suivant une séquence "voie 1") - Voie 1 (passage direct) : moyenne (tO+12 à tO+14) • Pour le capteur 16 on a :- Channel 2 (trapping): 0.5 x [average (tO + 7 to tO + 9) + average (t0 + 17 to tO + 19)] (average of the signals of the "channel 2" sequences preceding and following a sequence " channel 1 ") - Channel 1 (direct passage): medium (tO + 12 to tO + 14) • For sensor 16 we have:
- Voie 2 (piegeage) : 0,5 x [moyenne (to+7 à t0+9) +moyenne ( t0+17 à t0+19)] (moyenne des signaux des séquences "voie 2" précédant et suivant une séquence "voie 1")- Channel 2 (trapping): 0.5 x [average (to + 7 at t 0 +9) + average (t 0 +17 to t 0 +19)] (average of the signals of the "channel 2" sequences preceding and following a "channel 1" sequence)
- Voie 1 (passage direct) : moyenne (t0+12 à to+14)- Channel 1 (direct passage): average (t 0 +12 to to + 14)
L'influence des variations de teneur en eau sur le capteur 15 est corrigée très simplement en affectant l'écart des signaux "voie 1-voie 2" mesuré sur le capteur 16 d'un coefficient S représentant le rapport des sensibilités respectives à l'eau de ces deux capteurs, c'est-à-dire le rapport des pentes des deux courbes de réponse dans un domaine d'humidité allant de 5000 à 25000 ppm.The influence of the variations in water content on the sensor 15 is very simply corrected by assigning the difference in the signals "channel 1-channel 2" measured on the sensor 16 by a coefficient S representing the ratio of the respective sensitivities to the water from these two sensors, i.e. the ratio of the slopes of the two response curves in a humidity range from 5000 to 25000 ppm.
Les réponses des capteurs 15 et 16 (tensions brutes différentielles en volts) dans les domaines des teneurs en eau extrêmes rencontrées en air extérieur est donnée dans le tableau 1 en fin de description. L'équation de la courbe de variation (assimilée à une droite) de ce rapport en fonction de la teneur en eau est : Coefficient S = 2.10_5[H2O]The responses of sensors 15 and 16 (differential gross voltages in volts) in the fields of extreme water contents encountered in outdoor air are given in table 1 at the end of the description. The equation of the variation curve (assimilated to a straight line) of this ratio as a function of the water content is: Coefficient S = 2.10 _5 [H 2 O]
Les variations de teneurs en eau au niveau du capteur 15, en aval de la cartouche 12, sont comprises entre 0 et + 6000 ppm ; un rapport fixe de 1,67 est donc retenu entre les tensions brutes délivrées par les capteurs 15 et 16 pour une même teneur en eau . La valeur de 1,67 correspondant à l'écart maximal de teneur en eau est retenue préférentiellement à un coefficient moyen, car elle permet une meilleure adéquation de correction dans la mesure où, seuls les écarts élevés ont une incidence notable sur les résultats. On obtient ainsi après correction de la réponse à la teneur en eau du capteur 15 :The variations in water contents at the level of the sensor 15, downstream of the cartridge 12, are between 0 and + 6000 ppm; a fixed ratio of 1.67 is therefore retained between the raw voltages delivered by the sensors 15 and 16 for the same water content. The value of 1.67 corresponding to the maximum difference in water content is preferably used at an average coefficient, because it allows a better adequacy of correction insofar as, only the large differences have a significant impact on the results. After correction of the response to the water content of the sensor 15, we thus obtain:
COV (en mg/m3 de HCHO) = Kx x (Δ (V1-V2 ) 2620-l , 67 x Δ(V1-VOC (in mg / m 3 of HCHO) = K x x (Δ (V1-V2) 2620 -l, 67 x Δ (V1-
V2)2180) où Ki est la pente de la réponse du capteur 15 aux COV.V2) 2180 ) where Ki is the slope of the response of sensor 15 to VOCs.
Si le second terme permet de corriger la réponse à l'eau du capteur 15, la différence "voie 1- voie 2" du premier terme permet de corriger la réponse de ce capteur au CO non piégé par la cartouche 12 et de s'affranchir d'éventuelles dérives de zéro du capteur 15 dans le temps.If the second term makes it possible to correct the response to water from the sensor 15, the difference "channel 1- channel 2" of the first term makes it possible to correct the response of this sensor to the CO not trapped by the cartridge 12 and to overcome possible zero drifts of the sensor 15 over time.
Un calibrage est réalisé par injection et vaporisation de quantités connues de HCHO en solution aqueuse à 37% ; le tableau 2 en fin de description fournit les valeurs des signaux après traitement décrit ci-dessus. La courbe de calibration est une droite dans un domaine de concentration compris entre 0 et 6 mg/m3.Calibration is carried out by injection and spraying of known quantities of HCHO in 37% aqueous solution; Table 2 at the end of the description provides the values of the signals after processing described above. The calibration curve is a straight line in a concentration range between 0 and 6 mg / m 3 .
Dioxyde de carbone/capteur 21Carbon dioxide / sensor 21
L'équation de la courbe de calibrage est du type : C02 en ppm = a x E + b dans laquelle E représente le signal exprimé en volts (0-10 V pour 0-2000 ppm) . ETABLISSEMENT D'UN INDICE DE QUALITE DE L'AIRThe equation of the calibration curve is of the type: C0 2 in ppm = ax E + b in which E represents the signal expressed in volts (0-10 V for 0-2000 ppm). ESTABLISHING AN AIR QUALITY INDEX
Diverses approches pour l'établissement d'un tel indice peuvent être envisagées ; une solution consiste à comparer la teneur mesurée de chacun des composés sélectionnés : H20, CO, N02 , HCHO, C02 à différents seuils comme dans la grille du tableau 3.Various approaches for establishing such an index can be envisaged; one solution consists in comparing the measured content of each of the selected compounds: H 2 0, CO, N0 2 , HCHO, C0 2 at different thresholds as in the grid in Table 3.
Les niveaux de concentration susceptibles d'être atteints par chacune de ces teneurs sont répartis en 10 classes établies à partir soit de seuils réglementaires lorsqu'ils existent, soit de recommandations de l'Organisation Mondiale de la Santé pour la protection de la santé et constituent chacun un indice élémentaire. L'indice global est représenté par l'indice le plus grand des indices élémentaires correspondants à chacun des composés sélectionnés.The concentration levels likely to be reached by each of these levels are divided into 10 classes established either from regulatory thresholds where they exist, or from recommendations of the World Health Organization for the protection of health and constitute each a basic clue. The overall index is represented by the largest index of the elementary indices corresponding to each of the selected compounds.
Un exemple d'indice de CO est le suivant : Limite réglementaire en ambiance de travail : 50 ppm sur une période de 8 h .An example of a CO index is as follows: Regulatory limit in the working environment: 50 ppm over an 8-hour period.
Recommandations OMS : 60 mg/m3 (≈ 50 ppm) pendant 30 minWHO recommendations: 60 mg / m 3 (≈ 50 ppm) for 30 min
30 mg/m3 (25 ppm) pendant 1 h 10 mg/m3 ( 5 ppm) pendant 8 h Maximum retenu pour l'indice 20 ppm (23 mg/m3 <= indice 10 De même un indice 10 correspond à :30 mg / m 3 (25 ppm) for 1 h 10 mg / m 3 (5 ppm) for 8 h Maximum used for the 20 ppm index (23 mg / m 3 <= index 10 Similarly, an index 10 corresponds to:
- 1 mg/m3 de COV exprimés en équivalents HCHO (0.8 ppm à 20°C)- 1 mg / m 3 of VOC expressed in HCHO equivalents (0.8 ppm at 20 ° C)
- 200 μg/m3 de N02 (109 ppb à 20°C) - 2000 ppm de C02 (3667 mg/m3) Tableau 1- 200 μg / m 3 of N0 2 (109 ppb at 20 ° C) - 2000 ppm of C0 2 (3667 mg / m 3 ) Table 1
Figure imgf000022_0001
Figure imgf000022_0001
Tableau 2Table 2
Figure imgf000022_0002
Tableau 3
Figure imgf000022_0002
Table 3
Figure imgf000023_0001
Figure imgf000023_0001

Claims

REVENDICATIONS
1. Analyseur en continu de composés organiques volatils caractérisé en ce qu'il comprend : - un module de mesure comportant un premier capteur de CO/COV (15) et un second capteur de H20 (16) ,1. Continuous volatile organic compound analyzer characterized in that it comprises: - a measurement module comprising a first CO / VOC sensor (15) and a second H 2 0 sensor (16),
- un circuit de traitement séquentiel de l'air comportant : • un filtre (11) ,- a sequential air treatment circuit comprising: • a filter (11),
• une cartouche (12) de rétention sélective des composés organiques volatils disposée sur une première voie (12) en parallèle avec une seconde voie (11) directe, • une électrovanne (13) commandée par un sequenceur (14), qui assure la commutation première voie - seconde voie,• a cartridge (12) for selective retention of volatile organic compounds disposed on a first channel (12) in parallel with a second direct channel (11), • a solenoid valve (13) controlled by a sequencer (14), which ensures the switching first way - second way,
• une pompe (17) située en aval des capteurs (15, 16) de manière à ce que l'air à analyser soit aspiré à travers le filtre (11) et soit transféré vers les capteurs CO/COV (15) et H20 (16) soit directement, soit après passage à travers la cartouche (12) ,• a pump (17) located downstream of the sensors (15, 16) so that the air to be analyzed is sucked through the filter (11) and is transferred to the CO / VOC sensors (15) and H 2 0 (16) either directly or after passing through the cartridge (12),
- un circuit (18) de traitement des signaux provenant des capteurs (15, 16) et du sequenceur (14), permettant d'accéder aux trois paramètres suivants :- a circuit (18) for processing the signals from the sensors (15, 16) and the sequencer (14), allowing access to the following three parameters:
- la teneur en eau de l'air,- the water content of the air,
- la teneur en CO de l'air sur un échantillon débarrassé des COV, - la teneur en COV, en opérant une différence de signaux obtenus grâce au capteur de CO/COV (15) lorsque l'air à analyser est transféré vers celui-ci soit au travers de la première voie soit au travers de la seconde voie.- the CO content of the air on a sample free of VOCs, - the VOC content, by operating a difference in signals obtained thanks to the CO / VOC sensor (15) when the air to be analyzed is transferred to it either through the first channel or through the second channel.
2. Dispositif d'évaluation en continu de la qualité de l'air ambiant intérieur comprenant un analyseur en continu de composés volatils selon la revendication 1, dans lequel le module de mesure comporte également les éléments sensibles de capteurs de N02 (20) et de C02 (21) , et dans lequel le circuit de traitement séquentiel de l'air aspiré par la pompe à travers le filtre (11) balaye tout d'abord le troisième capteur (20) et le quatrième capteur (21) avant d'être transféré vers le premier capteur (15) et le second capteur (16) au travers de la première ou deuxième voie .2. A device for continuously evaluating the quality of indoor ambient air comprising a continuous volatile compound analyzer according to claim 1, in which the measurement module also includes the sensitive elements of NO 2 sensors (20) and of C0 2 (21), and in which the circuit for sequential treatment of the air sucked by the pump through the filter (11) first scans the third sensor (20) and the fourth sensor (21) before d '' be transferred to the first sensor (15) and the second sensor (16) through the first or second channel.
3. Dispositif selon la revendication 2, dans lequel le premier, le second et le troisième capteurs (15, 16, 20) sont des microcapteurs chimiques à oxydes métalliques.3. Device according to claim 2, wherein the first, the second and the third sensors (15, 16, 20) are chemical microsensors with metal oxides.
4. Dispositif selon la revendication 2, dans lequel la pompe (17) est une pompe à membrane.4. Device according to claim 2, wherein the pump (17) is a diaphragm pump.
5. Procédé d'évaluation en continu de la qualité de l'air ambiant intérieur, mettant en œuvre le dispositif selon l'une quelconque des revendications 2 à 4, et qui comporte les étapes suivantes : - on détermine la courbe de calibrage, de chacun des capteurs (15, 16, 20, 21) de mesure des différents composés : CO/COV, H0, N02 et C02 ,5. A method for continuously evaluating the quality of indoor ambient air, implementing the device according to any one of claims 2 to 4, and which comprises the following steps: - the calibration curve of each of the sensors (15, 16, 20, 21) for measuring the various compounds is determined: CO / COV, H0, N0 2 and C0 2 ,
- on corrige par calcul l'influence des composés interférants majoritaires,- the influence of the majority interfering compounds is corrected by calculation,
- on transpose le signal de sortie de chaque capteur en teneur de composé mesuré, en tenant compte de sa courbe de calibrage,- the output signal of each sensor is transposed into the content of the measured compound, taking into account its calibration curve,
- on détermine un indice de qualité pour chaque composé mesuré en faisant référence à une grille d'évaluation qui donne une valeur d'indice pour chaque composé en fonction de différents seuils de teneurs de composés se référant à des données sanitaires,a quality index is determined for each compound measured by referring to an evaluation grid which gives an index value for each compound as a function of different thresholds of content of compounds referring to health data,
- on obtient un indice global de la qualité de l'air en fonction des différents indices composés obtenus .- an overall index of air quality is obtained as a function of the various composite indices obtained.
6. Utilisation du dispositif selon l'une quelconque des revendications 2 à 4 pour le pilotage d'une installation de ventilation. 6. Use of the device according to any one of claims 2 to 4 for controlling a ventilation installation.
PCT/FR2001/000695 2000-03-09 2001-03-08 Continuous analyzer of volatile organic compounds, device and method for continuously assessing the quality of inside ambient air and use of said device for monitoring a ventilation installation WO2001067092A2 (en)

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