EP2106549A1 - Dispositif et procede de mesures couplees permettant un suivi global et en continu de traces de goudrons presentes dans un flux gazeux - Google Patents
Dispositif et procede de mesures couplees permettant un suivi global et en continu de traces de goudrons presentes dans un flux gazeuxInfo
- Publication number
- EP2106549A1 EP2106549A1 EP07858227A EP07858227A EP2106549A1 EP 2106549 A1 EP2106549 A1 EP 2106549A1 EP 07858227 A EP07858227 A EP 07858227A EP 07858227 A EP07858227 A EP 07858227A EP 2106549 A1 EP2106549 A1 EP 2106549A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tars
- gas
- detector
- measurement
- pid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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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
- G01N33/0027—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
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2247—Sampling from a flowing stream of 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
- G01N33/0006—Calibrating gas analysers
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/18—Injection using a septum or microsyringe
Definitions
- the present invention relates to the field of techniques for analyzing and measuring pollutants in a gas stream. More particularly, it relates to a device and method for continuously measuring the tars of a gas, these tar may be in the form of traces.
- the evaluation of the specifications of the synthesis gas requires knowing the composition of the gas and therefore, among other things, the concentration of the different polluting species; they are sulfur, nitrogen, chlorine compounds, alkali metals, dust and tars.
- Tars can pose other problems especially in pyrolysis or gasification reactors where under the action of heat, they give rise to a deposit of heavy hydrocarbon compounds, called coke, on the reactor walls; this phenomenon is called coking. Following this deposition, the heat transfers to the reactor are reduced. The formation of coke also tends to increase the pressure losses in the ducts and in the absence of corrective action eventually clogs the pipes.
- a first difficulty is related to the meaning of the generic term "tar”, which differs according to the field of application considered.
- tars In the context of air pollution, metallurgy, waste incineration, co-generation and the production of synthetic fuels, the term “tars” is generally used to refer to all organic compounds having a molecular weight greater than that of benzene - 78 g / mol - but there is no official definition for this term, and the literature reports about thirty definitions for the word "tar”
- the tars cover a broad spectrum of species (more than 2000) whose physicochemical characteristics (polarity, volatility, molar mass, chemical affinity) vary over a wide range of values, which makes it particularly difficult to obtain measurement showing the total content of tars.
- Physicochemical characteristics polarity, volatility, molar mass, chemical affinity
- Several classifications of these different compounds have been proposed so far, such as the classification of Milne & Evans (1998) which lists the different tars in three classes:
- Class 1 primary species
- Class 2 secondary species
- Class 3 tertiary species
- the main components are polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs) and phenols.
- PAHs polycyclic aromatic hydrocarbons
- VOCs volatile organic compounds
- phenols phenols
- the device must be able to provide a measurement every minute, or at least the measurement occurrence must be compatible with a monitoring that can be considered as continuous (of the order of a minute) including trace concentrations;
- - take an on-line measurement of the tars concentration or at least carry out the measurement under conditions of temperature and pressure as close as possible to those prevailing in a main pipe in which flows a synthesis gas to be analyzed. This is to avoid any significant change in the tars concentration by a change in value of the temperature and pressure parameters.
- the gas to be measured has a temperature of approximately 300 ° C .;
- the methods proposed to date for the determination of the tar concentration of a gas can be divided into four main families: - a first family which groups together so-called "spectrometric” methods, which consist in the detection and analysis of a spectrum. These include, for example, infrared, ultraviolet (UV) or luminescence spectrometry, Laser-Induced Breakdown Spectroscopy (LIBS) or mass spectrometry.
- UV absorption which is very close to that of infrared absorption, is that water vapor does not interfere with UV.
- the latter is used for example for the detection of polycyclic aromatic hydrocarbons in contaminated soils as mentioned in patent EP0446975 entitled "Installation of the rapid analysis of tar components and method for such an analysis”.
- Patent WO9833058 relates to a method for the on-line analysis of polycyclic hydrocarbons by collecting aerosols by means of a filter and subjecting it to excitation via UV radiation. It is then a question of comparing the spectral image obtained with the different spectra listed in a database.
- Another technique commonly used in the continuous control of combustion gases is FTIR (Fourier Transform InfraRed) infrared spectrometry.
- FTIR Fastier Transform InfraRed
- Various documents evoke this technique such as for example the documents WO2006015660, WO03060480 and US5984998.
- the literature does not mention a possibility of measuring tars, the products commonly followed being CO, CO 2 , O 2 , H 2 and H 2 O.
- Patent WO030227650 relates to the use of the Laser-Induced Breakdown Spectroscopy (LIBS) technique for the detection of polycyclic aromatic hydrocarbons (PAHs) and monoaromatics. This fast method is suitable for monitoring PAHs.
- LIBS Laser-Induced Breakdown Spectroscopy
- PAHs polycyclic aromatic hydrocarbons
- PAHs polycyclic aromatic hydrocarbons
- monoaromatics This fast method is suitable for monitoring PAHs.
- the LIBS technique consists in vaporizing and ionizing in the form of plasma the species sampled by means of a laser.
- One of the limits of the flame ionization technique is the disturbance of the measurement by combustible gases such as CH 4 and H 2 , which constitutes a real limitation insofar as the synthesis gas is a mixture of CO and H 2 and that it also contains methane.
- the response depends on the oxygen content of the gas to be measured.
- the measurement of organic compounds by flame ionization requires as well as measurement by photoionization to know the composition of tars and the response factors of the various compounds to obtain a quantitative measure of total tars. Indeed the intensity of the response depends on the given species, which therefore requires to involve a correction coefficient.
- Photo-ionization unlike the flame ionization technique, is a non-destructive method of measurement.
- the presence of methane which is troublesome in the case of an FID measurement, does not pose a problem in the case of measurement by photoionization because the ionization potential of methane (12.6 eV) is lower than the power of the bulb, which makes the methane undetectable to the PID.
- the photoionization as well as the flame ionization technique is particularly suitable for continuous measurement. These two techniques give an overall value of the species that it is desired to measure but this value is given in equivalence with respect to a reference compound, for example isobutylene in the case of the use of a detector by photoionization .
- the photo-ionization measuring devices are not designed to be able to measure hot gases (temperature limit of the order of 60 ° C.), since their main application lies in the measurement of pollutants, in particular that of PAHs. and VOCs in the air. Therefore these devices are revealed unsuitable for measuring tars in a hot environment, charged with particles (need to interpose one or more filters) and moisture, to which they are sensitive. In the absence of knowledge of the composition of tars and the response factors of the various compounds, the measurement by photoionization or by flame ionization no longer allows a continuous measurement of the total concentration of tars.
- An electrochemical cell consists of a membrane permeating the compounds to be analyzed; on the other side of the membrane is a liquid electrolyte which, in the presence of the species to be detected, generates an oxidation-reduction reaction at the origin of a measurable electric current.
- This device is not adapted to a measurement in temperature, moreover the selectivity of the membrane is not compatible with the sampling of a large number of components whose physicochemical properties vary over a wide range of values.
- Semi-conductor sensors have similar limitations in terms of temperature resistance, but they can measure a greater number of pollutants.
- the most commonly used techniques are chromatography in the liquid phase or in the gas phase.
- the most commonly used techniques in the case of tar measurement are the FID flame ionization detector and the Mass Spectrometer MS. The latter is commonly used for the analysis of the combustion gases of steelworks.
- the use of a mass spectrometer is not very suitable for carrying out a quantitative measurement of the tars present in the state of traces, even by carrying out numerous calibrations. In fact, the low repeatability of the measurements for the case of the measurement of organic compounds such as tars makes it impossible to quantitatively monitor traces of tars.
- the SPME technique developed by Dr. Pawliszyn in the 1990s consists of the absorption and / or adsorption of chemical species on a support covered with an absorbing and / or adsorbent species. It is a fused silica fiber coated with a polymer, such as divinylbenzene (DVB), carboxene, polydimethylsiloxane (PDMS), etc. or a mixture of these compounds.
- a polymer such as divinylbenzene (DVB), carboxene, polydimethylsiloxane (PDMS), etc. or a mixture of these compounds.
- This sampling step may pose a problem as to the representativeness of the sampling due to the more or less selective nature of the adsorbent and / or the absorbent.
- This selectivity is linked to many parameters that determine the physico-chemical affinity between a sampled molecule and the adsorbent / absorbent substance.
- the main mechanism which is involved is adsorption, there may be adsorption competitions at the level of the different species to be sampled.
- a fiber such as polydimethylsiloxane fibers (PDMS) overcomes this problem since this substance behaves like a liquid (vis-à-vis the sharing of tars between the PDMS phase and the matrix gaseous) and thus involves an absorption mechanism which, unlike adsorption, does not cause competition between the species to be sampled.
- the sampling is representative since there exists at equilibrium a relation of proportionality between the initial concentration of the compound (i) in the matrix to be sampled and the mass of compound ( i) adsorbed / absorbed on the fiber provided that the sampling volume is sufficiently large.
- the temperature limit of the SPME fibers is usually between 240 and 340 ° C.
- the patent WO0017429 entitled "solid phase micro-extraction fiber structure and method of making” reports on a process making it possible to obtain PDMS fibers having a holding capacity of temperature may be greater than 360 ° C.
- Even in the presence of automatic sampling systems such as automatic passers, the duration of the measurement using a chromatograph coupled to a detector is not suitable for continuous measurement traces of tars.
- Patent EP0586012 proposes a device for measuring the content of certain hydrocarbons which may be present in tars (line 5 of page 2), which consists in taking samples by an adsorption device and in pass them through separation, extraction and measurement means that may include a chromatograph or a mass spectrometer.
- the method implemented by this device requires the use of solvent to elute the tars adsorbed on the adsorbent / absorbent solid used for the concentration step.
- This device does not make it possible to carry out a continuous analysis of the tars and also does not allow a measurement of all the types of tars because of the selectivity of the preparation.
- None of the solutions presented is therefore capable of satisfying the following requirements: a continuous, quantitative, total and on-line measurement of tar traces (detection threshold less than mg / Nm 3 ). None of the devices presented is able to perform a measurement of the total concentration of tars continuously with a measuring occurrence of the order of one minute. Moreover, the devices presented do not measure all the tars, whether they are in the solid phase or in the gaseous state.
- the objective pursued is to carry out a quantitative and continuous measurement of all the tars present in the solid phase or in the gaseous state in a gaseous flow at temperature.
- the measurement must be representative of the total concentration of tars prevailing in a main pipe in which a synthesis gas flows under given temperature and pressure conditions.
- total concentration is meant the concentration incorporating all the tars as defined above.
- Trace tars are tars with a total concentration of a few milligrams per normal cubic meter or less).
- the present invention proposes a coupling of methods for measuring tars in the gas phase, one being discontinuous and a priori partial, the other continuing but difficult to interpret with regard to its raw data alone.
- This coupled device can be more or less sophisticated depending on the fineness of the information sought.
- this relates to a device for continuously measuring the tar concentration of a gas, characterized in that it comprises a first measurement line and a second measurement line, the first line measuring device being equipped with a first detector and the second measurement line being equipped with a second detector and means for extracting gas samples and means for separating the gas tars components upstream of the second detector.
- a first measurement line performs a continuous measurement and a second measurement line performs sampling which makes it possible to regularly calibrate the results obtained by the first measurement line by calculating a global correction coefficient derived from a law of mixtures.
- the means for extracting gas samples comprise, in a preferred embodiment of the invention, a reversible absorption or adsorption tar, which may be in a preferred embodiment, an SPME fiber or a set such fibers.
- a PDMS fiber will be chosen.
- a difficulty of the measurements comes from the presence of moisture in the gas.
- the sample extraction means of the gas then also comprise a sampling bulb where the gas samples stay; the fiber is housed in a syringe passing through a stopper of the ampoule and slides therein so as to extend into the ampoule until the tars of gas contained in the ampoule are deposited on it.
- This kind of sampling device makes it possible to concentrate the tars present even in the state of traces in the gas and thus allows a more precise detection.
- the gas sample extracting means may be associated with a chromatographic column to separate the components of the tarmac mixture and, optionally, a mass spectrometer to recognize them.
- the tart mixture components then arrive at the detector of the second measurement line and their individual concentrations are measured.
- a calibration of the results given by the detector of the first measurement line from the moment of taking this sample then becomes possible.
- the detectors of the two measurement lines are preferably homogeneous and consist, in a preferred embodiment of the invention, of photo-ionization detectors (PID), or possibly flame ionization detectors (FID). Instead of a photo ionization detector (PID), a flame ionization detector (FID) may be preferred if the gas matrix is not likely to influence the measurement by burning up.
- detector 32 of the other measurement line B2 which should in any case be identical to this one.
- these detectors allow continuous measurements, so that they are particularly suitable for the measurement of very low concentrations of tar, that is to say in the form of traces, according to one of the main objectives of the invention.
- These detectors must also be insensitive to gases likely to disturb the measurement, (in particular) hydrogen, carbon monoxide and methane that may be present in the gas, and which are actually present in the synthesis gases from the gasification of biomass. This problem has been solved by choosing a particular ionization energy range to avoid the ionization of these gases, preferably between 10 and 11 eV, and more preferably 10.6 eV. The invention can therefore advantageously be applied to such gases.
- Another optional aspect of the invention is the presence of a calibrated tarmac generator that is connected to the first measurement line and the second measurement line.
- This generator makes it possible to carry out a calibration of the apparatuses and to calculate different coefficients necessary for obtaining a quantitative measurement which will be representative, according to criteria which it is possible to adapt according to the fineness of the desired measurement, of the total concentration of tars present in the gas stream.
- This generator of tarmac atmospheres may comprise a liquid tar tank and a gaseous stream device passing through the tank, and finally a device located at the inlet of the tank for dividing the gaseous stream into bubbles in the tank: this device exploits the liquid balance - tars gas and causes a portion of the contents of the tank in the gas stream also gaseous form. Sampling on products physically comparable to those to be measured will normally be of good quality.
- Another aspect of the invention is related to the temperature and pressure conditions of the gas. It is advantageous for the first line and the second line to be provided with heat-insulated ducts in order, in particular, to avoid condensations of tars.
- measurements depend on temperature and pressure gases. Humidity also has an influence on the detectors of the measuring lines, but its influence on the coefficients connecting the results of the two lines is low if the pressure and the temperature of the gas flow remain constant. In addition, the water content remains fairly stable in practice in most applications.
- the first measurement line of temperature and gas pressure adjustment means upstream of the detector, especially in the case of a photoionization detector, which is not designed to work at a temperature very high. Adjustments in temperature or pressure of a gas stream may therefore be necessary. Moreover, the agreement between the two measurement lines depends on coefficients which themselves depend on the measurement temperature, so that it may be appropriate to maintain the temperature of the gas flow at a constant value. Similarly, the temperature and especially the pressure of the gas stream can be adjusted in the second measurement line, in particular because the absorption or the adsorption of the samples are easier at higher pressure.
- the second measurement line may then comprise an enclosure for conditioning the pressurized gas in front of the sample extraction means.
- An originality of the invention is the use of a PID or FID sensor for continuously measuring a gas whose tar content has an unknown and variable composition, whereas such Detectors, if known to be suitable for continuous measurement, are normally used only for measuring compounds having known compositions.
- Another originality of the invention is the use in parallel of two measurement lines interconnected by a processing unit which synchronizes them and exploits them by pulling from one a calibration coefficient, called here coefficient of response, of the detector continuously to express the measurement of this detector, and periodically renewing this coefficient.
- Yet another novel feature of the invention is the use of a PID or FID detector for the second measurement line, which performs discontinuous measurements, whereas such detectors are not preferred for such measurements because of their accuracy. smaller ; but their rapid measurements allow frequent and directly usable sampling for the other detector.
- Two identical detectors will therefore be used in the invention, that is to say which measure the same physical phenomenon (photo-ionization or flame ionization), without the identity of the detectors having to extend to all their details. manufacturing for example.
- Still another novel feature of the invention is to obtain tar samples in a sufficiently concentrated state to give a satisfactory calibration even when they are in a trace state.
- Another originality is the use of a sampling criterion based solely on pre-dominant tars so as not to slow down the calibration of the detector continuously or to make it impossible, at the cost of an accepted uncertainty of the measurement.
- another originality of the invention is the verification of a criterion of coherence between the measurements of the continuous detector and measurements of the detector in a sequential manner, so as to allow correction of the calibration if the coherence is insufficient.
- the invention finally makes it possible to measure on gases of between 25 ° C. and 500 ° C., and 1 bar and 10 bars of pressure, in particular.
- another aspect of the invention is a method for continuously measuring the total concentration of tars, which may even be in the form of traces, of a gas, characterized in that it comprises:
- first detector which is a photo-ionization or flame ionization detector
- the method advantageously comprises species selection by retaining only predominant species in the gases for sampling.
- a periodic estimate of the total tarsal concentration by the second sensor is made, as well as a comparison of this periodic estimate with a simultaneous estimate derived from the continuous estimates of the total tars concentration. A failure of this comparison can then command a complement of the chosen species selection.
- FIG. 1 schematically represents a device according to the invention, whose objective is the continuous measurement of the tars present in the gaseous or solid state in a gaseous flow in temperature;
- FIG. 2 is a device for generating tar vapors which allows between others to calibrate the different detectors as well as the SPME fiber;
- FIG. 3 represents a block diagram of the various calculation steps leading to the determination of the total concentration of tars
- FIG. 4 is a graph showing the absorption kinetics of several tars on a 100 ⁇ m diameter PDMS fiber at the temperature of 80 ° C. and at a pressure of one bar;
- FIG. 5 represents a graph showing the evolution of the mass extracted from tars i on an SPME fiber as a function of the exposure time thereof and for different temperatures.
- FIG. 1 there is schematically represented a device dedicated to the measurement of tars present in the solid state and in the gaseous state.
- the gaseous mixture to be analyzed flows inside a main pipe P made of stainless steel, for example AISI 310 or AISI 316.
- a main pipe P made of stainless steel, for example AISI 310 or AISI 316.
- the alloys based on nickel and chromium are commonly used as the material constituting conduits capable of withstanding temperatures of 1200 ° C. and above and have the advantage of having a very weak catalyst effect for the formation of coke, which makes it possible to limit the deposition of coke or soot on the internal surfaces of the pipes.
- Said pipe P comprises means 70 and 71 for continuously measuring the pressure P p and the temperature T P reigning in it.
- the nature and the composition of the gas mixture vary according to the intended application.
- the predominantly present species are CO and H 2 , these two compounds constitute the gaseous matrix.
- gases such as CO 2 , CH 4 , H 2 O and various pollutants including tars.
- the gas flow upstream of the Fischer-Tropsch process is at a temperature of about 300 ° C. and at a pressure of up to 30 bar.
- the overall measurement device comprises two devices, the first of which is assigned to the discontinuous measurement of tars in the solid phase and the second to the continuous measurement of tars in the gaseous state. It is this second device for continuous measurement of tars in the gaseous state which is the subject of the invention and which will be mainly described; the first device is optional and is a simple auxiliary to complete the measurement.
- the first device for the measurement of tars in the solid phase comprises an isokinetic sampling device 1 according to ISO 9096 and / or ISO 2066.
- the isokinetic sampling 1 is connected by stainless steel metal conduits A and a valve of sectioning 2 on these ducts A to a particle sorting member such as for example a cyclone 3 or a set of cyclones which operates the separation between particles larger than a few ⁇ m, in particular the particles of coal or "char", sub- products of the pyrolysis of biomass, and the smaller-sized particles such as soot resulting from the polycondensation of tars.
- Said soot is then collected by impaction on a filter medium 4 so as to be in a second time weighed. All the ducts of this device is heat-insulated and maintained at the temperature Tp of the main pipe in order to avoid the condensation of tars present in the gaseous state in the main stream.
- the second device intended for the continuous measurement of gaseous tars, consists of four major subassemblies which are: a system for sampling and conveying gases (5, 6, 7, 8, 9 and 10); a calibration device (28, 19, 20 and 21); a first measurement line B1 (29, 30, 31, 32, 33, 34 and 35), dedicated to the continuous measurement of the total concentration of tars, given in equivalence with respect to a reference compound; a second measurement line B2 (11, 12, 13, 14, 15, 16, 17, 18, 22, 23, 24, 25, 26 and 27), which makes it possible to re-calibrate and validate or invalidate the measurement from the first measurement line; and a set dedicated to data processing (36).
- the gas sampling and conveying system (5, 6, 7, 8, 9 and 10) is located downstream of the isokinetic sampling system 1 so as not to disturb the isokinetic sampling system 1.
- the gas sampling and conveying system is heat - insulated and maintained at the temperature T p in order to avoid creating "cold zones" which would favor the condensation of the tars. It is also a question of routing the gas to be analyzed until the two measuring lines B1 and B2 under conditions of temperature and pressure as close as possible to those prevailing in the main pipe P in order to avoid condensation and reactions of the tars. he It is therefore necessary to have a measurement of the concentration of tars present in the gaseous state which is as representative as possible of that existing in the main pipe P.
- the temperature maintenance of the pipes and various other elements (7, 9 and 10) can be done by means of an electric heating device or by circulation of hot nitrogen around said conduits and other organs for conveying the gas to be analyzed.
- the sampling system comprises a frit 5 which may be metallic.
- the constituent material of the frit must be carefully selected to limit the catalytic effect leading to the formation of coke and thus the destruction of tars; it may be for example a material formed based on silicon carbide.
- the frit 5 can just as well and this without limitation being made of quartz, ceramic or fiberglass. Said frit 5 is maintained in temperature by means of a heating device in order to avoid the condensation of tarry compounds favored in particular by the pressure loss that it induces.
- the frit 5 serves as a filter for the solid particles but allows a portion of the gas flow to flow into a sampling line B leading to the measurement lines B1 and B2.
- the sampling pipe B is insulated and maintained at the temperature T p of the flow in the main pipe P.
- a shutoff valve 7 placed downstream of the frit 5 makes it possible to isolate the sampling pipe B from the main pipe P.
- the gas sampling and routing system comprises means 72 and 73 making it possible to measure the temperature and the pressure within the sampling line B.
- a purge duct 8 makes it possible to purge all the measurement lines B 1 and B 2. B2 which will be described later.
- An expansion valve 9 placed on the sampling line B makes it possible to lower and maintain constant pressure in lines B1 and B2.
- a flow limiter 10 makes it possible to adjust the flux ⁇ d 2 as needed.
- the calibration device (28, 19, 20 and 21) will now be described with reference to FIGS. 1 and 2.
- the calibration device comprises: a tar atmosphere generator 28 which makes it possible to generate standard atmospheres of tars to calibrate the measurement; a multi-channel valve 20 with its vector gas supply system 19 and a column 21 of capillary column type for gas chromatography.
- the multi-port valve 20 is designed to inject the carrier gas 19 and the gas originating from the tarmac generator 28 by a line BI1 towards the column 21 and to a photo-ionization detector 26 by a pipe
- the tarmac atmosphere generator 28 will now be described with reference to FIG. 2.
- the generator 28 comprises: a tar supply system (45, 46, 47, 54, 55); a liquid-gas equilibrium vapor generator (50, 57, 58, 60 and 61); a subset of post-processing of the generated atmospheres (41, 43, and 44); and a servo system (42, 48, 51, 52, 53, 56 and 59) for controlling the amount of vaporized tars.
- the feed system comprises tanks (45 and 47) storing tars in liquid form which are conveyed to a thermostatic bath 57 by means of peristaltic pumps (54 and 55). The different tanks are supplied by a supply port 46 or 106.
- the steam generator comprises a pressurized nitrogen supply 61 provided with a non-return valve 60, both located at the bottom of the thermostated bath 57. Pressure measuring means 90 is added.
- Said bath thermostated 57 comprises a frit 58 disposed in its bottom. The role of the frit 58 is to create fine bubbles of nitrogen that will flow through the liquid mixture of tars while driving a portion of the latter. The vapors thus formed will escape through an outlet port 50.
- the purpose of the post-treatment sub-assembly is, among other things, to dilute the generated tar vapors in order to obtain atmospheres of low tar content.
- a feed under nitrogen pressure 41 is connected to a mixer 43 in which a stirring of the vapors of tars and inert gas takes place.
- An exchanger 44 is disposed downstream of said mixer 43 to modify the temperature of the generated atmosphere if necessary.
- the various pipes in which the atmosphere of tars flows are insulated and maintained in temperature. Said pipes are also provided with means 97, 98 and 99 dedicated to the measurement of temperature and pressure.
- a steam supply 63, placed upstream of the mixer 43, can be used to modify the water content of the generated tarmac atmospheres.
- the opening of a micrometer valve 94 located on a pipe connecting it to the mixer 43 allows this adjustment.
- the power supplies 41 and 63 are each provided with pressure measuring means 95 or 96 and a flow meter 42 or 64.
- the servo system comprises a microprocessor-type data processing unit 59 which regulates the temperature of the thermostated bath 57 by means of a heating device and a sensor, not shown here. Maintaining the level of liquid tars present in the bath 57 is ensured by monitoring the altitude of a magnetic float 11 by a position detector.
- the regulation of the position of the magnetic float 51 is carried out by controlling the flow rates of the tars measured by the flow meters 53 and 56, each disposed on a pipe leading from a tank 45 or 47 respectively of tars to the bath 57. Each of these pipes is still equipped with a delivery pump 54 or 55 and a shut-off valve 92 or 93.
- a pipe of back 48 from the bottom of the bath 57 and provided with a delivery pump 62 is able to return the tarry content of the bath 57 in one or other of the tanks 45 or 47 by a dispensing valve 95 or to unload it by another distribution valve 91.
- the bath 57 is provided with a temperature measuring device 107.
- the device shown in FIG. 2 is an exemplary embodiment of a generator of tarmac atmospheres 28 which is in no way limiting. This device is particularly suitable for tars that are in the liquid state under standard conditions of temperature and pressure (CSTP). In the case of tar in the solid state, a device involving a fixed bed of solid tars traversed by a carrier gas flow can be envisaged.
- CSTP temperature and pressure
- the measuring line B1 will now be described with reference to FIG. 1.
- the measurement line B1 comprises: four parallel processing channels B21, B22, B23 and B24 of the gas to be analyzed.
- the B21 channel comprises a pressure reducer 31 which makes it possible to lower the pressure as needed.
- Lane B22 comprises a filtering medium 30 for adsorbing / absorbing one or more molecules in a preferential manner, it may be water for example.
- the path B23 comprises a heat exchanger 29 which makes it possible to lower or on the contrary increase the temperature of the gas to be analyzed.
- Track B24 is unoccupied and insulated; a Photo Ionization Detector (PID) 32 that has been modified to withstand pressure and temperature; measuring means (78, 79 and 34) for continuously determining the temperature, the pressure and the flow rate.
- the flow is indicated by a volumetric meter 34.
- the line B2 ends up returning to the main pipe P to return the gas taken.
- a delivery pump 35 is responsible for establishing the sampled gas flow.
- the UV lamp of the PID 32 is chosen so that the ionization energy provided can not ionize other molecules than tars.
- the ionization energy provided by the lamp must be lower than the first ionization energies of the compounds other than tars, ie less than 14 eV and more wisely lower than that of oxygen (12.1 eV) so that one the presence of air is not a source of disturbance of the measurement.
- the PID 32 can suitably be adapted to temperature resistance levels (for example from 0 to
- a first provision is to have an optical interface, transparent to UV, as mentioned in patent WO1994027141 between the gas and the bulb. This is to protect the lamp vis-à-vis deposits of carbon compounds that have the effect of limiting the life and efficiency of the lamp. In the case of our application, it is also a question of limiting the transfers of heat of the gas towards the bulb in order to minimize the thermal stresses inherent to the measurement of a hot gas. It is also to protect the bulb from the pressure to the extent that the bulb is in depression; a measurement in pressure is likely to bring a better sensitivity of the apparatus because for a given volume of the ionization chamber, there are more ionized molecules;
- Another provision is to design mobile optical interface to allow the replacement thereof;
- Another provision is to use in the ionization chamber materials resistant to temperatures of the order of 400 0 C or higher; it may be for example ceramics for the walls and quartz for the optical interface.
- Another PID detector 26 that will be mentioned later can receive the same facilities.
- An air injection system 33 controls an air sweep circuit through the PID detector 32 to periodically clean accumulated deposits in the ionization chamber and on the optical interface.
- the measurement line B2 comprises: a conditioning chamber 11 making it possible to adjust the temperature and the pressure of the gas to be analyzed; - A sampling system comprising a thermostatic sampling bulb 12, one or more septum (s) 14, an SPME fiber 13 with its injection system which comprises a syringe 15 and an automatic feeder 22; a volumetric counter 16; a volumetric pump 17; a column 25 for capillary column gas chromatography; an injector 24 for SPME 13 fiber; a set of synchronized detectors which comprises a PID 26 (Photo Ionization Detector or photo-ionization detector) and a mass spectrometer 27;
- PID 26 Photo Ionization Detector or photo-ionization detector
- the conditioning chamber 11 makes it possible to adjust the pressure and the temperature of the gas to be sampled. Indeed the temperature and the pressure are both parameters that must be optimized in order to then allow optimal extraction of tars at the sampling bulb 12. Temperature measuring means 74 and pressure 75 equip the containment enclosure 11.
- the sampling system comprises a sampling bulb 12 which is thermostatically controlled, and also equipped with means for measuring temperature 76 and pressure 77.
- the inner surface of the ampoule is treated to limit the phenomena of adsorption (polished stainless steel for example).
- the ampoule is equipped with one or more septa 14 (leakproof plugs) allowing one or more SPME 15 (Solid Phase Micro Extraction) syringe to be introduced by introducing one or more fibers adapted to the temperature conditions and selected tars in the thermostated bulb 12. The tars will be progressively adsorbed / absorbed on the SPME fiber until the sorption equilibrium is reached. At equilibrium the mass of adsorbed / absorbed compounds is maximal.
- K (i) C ⁇ fl ((i) / C ⁇ ampou ie (i)
- the sampling ampoule 12 may be linked with the vacuum pump in order to impose a pressure adapted to the extraction of tars on the selected SPME fiber 13.
- the imposed temperature is between the maximum permissible temperature of the SPME fiber 13 (depending on the nature of the latter) and the sampling temperature allowing adsorption optimized, ie fast enough (ideally less than a minute) and ensuring sufficient sensitivity (ie to reach the target detection threshold of the sampling method). In fact, the higher the sampling temperature, the faster equilibrium conditions are reached and the lower the amount of compounds adsorbed.
- the autosampler 22 makes it possible to automate sampling by SPME. It also makes it possible to inject an SPME fiber into the thermostated ampoule 12 as into the injector 24 of the chromatograph 25.
- the chromatograph operates a separation of the various compounds as a function of their retention time in the capillary column.
- the spectrometer 27 is located after the column 25, it makes it possible to identify the tars extracted from the SPME 13 fibers. It makes it possible to go back a posteriori to the composition of the tars present in the gaseous mixture before sampling by the SPME 13 fiber considered from the measurements given by the PID 26 and formulas that will be described later ( Figure 3).
- the ionization energy of the PID lamp must be lower than the values of the energies. of ionization of permanent gas molecules (CO, H 2 , CO 2 and CH 4 ) constituting the gas matrix of the stream to be characterized.
- the information processing subassembly which consists of a computer unit 36 which makes it possible to acquire and process the data provided by the tar sensors that are the mass spectrometer 27 and the two PIDs. 26 and 32.
- This device implements in particular an algorithm ( Figure 3).
- the purpose of the computer unit 36 is to: identify the species of the separated tars at the outlet of the chromatograph 21 or 25 by means of the mass spectrometer 27. This identification is carried out on the basis of a comparison between the decomposition spectra given by the mass spectrometer 27 and those contained in a database.
- the identification tool integrated in the information processing device is a standard signal comparison element taking into account possible interferences (overlays) between the different spectra; associating with each of the compounds identified by the decryption of the mass spectra a quantitative measurement provided by its response to the PID 26.
- the latter is synchronized with the mass spectrometer 27; associate with the response of the PID detector 26 (thanks to a prior calibration) a concentration of each of the compounds previously identified in the gas flow of the line B 1.
- the Correspondence between the concentration on the SPME fiber 13 of each compound i and that in the sampling bulb 12 will have been previously evaluated by using the partition coefficients Kd) (determined for a given fiber, a temperature and a pressure) between the gas matrix and the SPME fiber 13 given; comparing the sum of the signals given by the PID 26 taking into account the SPME / GC / MS / PID correspondence with the overall signal given by the PID detector 32.
- the overall function of the information processing device 36 is to enable to continuously give a "true" quantitative measurement of all the tars present in the gaseous state in a flow of temperature and pressure.
- part of the main flow ⁇ p is taken from the isokinetic sampling device 1.
- the shutoff valve 2 is open and lets the withdrawn flow ⁇ d i which passes through the cyclone 3 where a separation between coal particles (or "char"), byproducts of the pyrolysis of carbon-rich biomass, and condensed tars.
- the tars are then conveyed in pipes maintained at the temperature T p to a filtering medium 4, where by impaction the already condensed tars are trapped.
- the temperature of the main line T p greater than 300 0 C, limits condensation of the gaseous tars on the filter medium 4.
- part of the main flow ⁇ p is diverted to a secondary flux ⁇ 2.
- the particles are trapped by the frit 5 maintained at the temperature T p .
- the intermittent operation of a feed 6 under nitrogen pressure to the frit 5 avoids the fouling of the latter.
- the isolating valve 7 isolates the measuring device of the main pipe P.
- the expander 9 is disposed upstream of the measurement lines B1 and B2 to lower the pressure to a level that is compatible with the latter. The operation of the measurement line 1 will now be described with reference to FIG.
- the conditioning enclosure 11 is depressed, as well as the sampling bulb 12 by a positive displacement pump 18.
- the valves 109 and 110 are then closed so as to isolate the sampling bulb 12 from the rest of the circuit.
- a valve 108 is then opened so that the enclosure 11 is filled by the diverted flow ⁇ d2 i.
- the autosampler 22 comes to place one or more syringes 15 each containing a retractable SPME 13 fiber through the various septa 14 of the sampling vial 12. Indeed we may be arranged to arrange in the bulb several identical or different fibers so as to optimize the extraction of all compounds.
- the chamber 11 makes it possible to operate a temperature and pressure conditioning of the sampled gas. Temperature and pressure are parameters to be optimized as will be described later.
- the valve 108 is then closed and the valve 109 open so that the gas contained in the chamber 11 fills the sampling bulb 12.
- the tars and other compounds will be absorbed on the SPME 13 fibers with a concentration , very useful for the subsequent measurement, tars on a small volume.
- the autosampler 22 comes to place the syringe 15 on the injector 24.
- the absorbed compounds will be desorbed thermally in the injector 24 in a relatively short time ( ⁇ 30s) and are driven through the column 25 by a carrier gas 19.
- An SPME 13 fiber can be reused approximately a hundred or more times. Regeneration of the fibers is carried out under a stream of nitrogen in a thermostatically controlled enclosure at 250 ° C. for 15 minutes.
- Vector gas such as helium originating from an injector 23 causes the various compounds desorbed in the chromatograph where they will be retained for a longer or shorter time in the column 25 according to their affinity with respect to the stationary phase of column 25 of the chromatograph gas.
- the retention time is characteristic of one or more species which will be identified by mass spectrometry as a well-defined compound.
- the quantity of the compound i is indicated by the signal delivered by the PID.
- the measurements on the fibers 13 can be performed before the sorption equilibrium has been reached to accelerate the sampling measurements at the expense of a loss of sensitivity; Moreover, it is possible to recommend the use of nanotube or nanostructure fibers to increase the mass of adsorbed tars, to increase the resistance of the fiber to temperature and to improve the desorption to the injector 24 for a better quality of the chromatographic peaks observed.
- the operation of the measurement line 2 will now be described with reference to FIG. 1. In normal operation, a part of the gas flow taken from the main pipe is routed to measurement line B2.
- the secondary flow ⁇ d22 will be routed to the line B21 or B23 where the expander 31 and the exchanger are respectively arranged.
- the filter medium 30 may be used to adsorb / absorb preferentially one or more components whose discrimination in the overall signal would be relevant.
- the flux ⁇ d 22 is then routed to the PID 32 which performs a continuous measurement or at least calculates an average value for a time interval of less than one minute.
- the signal delivered by the PID 32 Signal ° ot PID (32) is recalibrated every pT (T sampling period, p being a non-zero natural integer) by a correction coefficient CF m ⁇ xPID (32) which is considered as constant during a duration equal to the sampling period T and whose calculation will be explained later.
- a correction coefficient CF m ⁇ xPID (32) which is considered as constant during a duration equal to the sampling period T and whose calculation will be explained later.
- the response coefficients associated with the PID detectors 26 and 32 Before the response coefficients associated with the PID detectors 26 and 32 can be determined, it is necessary to calibrate the signal of the latter in advance with respect to a reference compound, which may be, for example, isobutylene.
- a reference compound which may be, for example, isobutylene.
- the response of the PID detectors being linear, two measuring points of the minimum PID detectors are necessary. They are determined from two atmospheres of known concentrations of isobutylene (for example 10 ppb v and 1000 ppb v ).
- the response of the detector signal varies according to the detected tar i. Indeed, this signal depends in particular on the ability of tar i to react the detector and therefore its ability to be ionized by the PID detector. This capacity is itself a function of the potential of first ionization, the nature of the molecule and the atomic bonds that compose it. It is therefore necessary, in order to be able to compare each signal induced by different compounds, to carry out a calibration making it possible to estimate the expected response of the PID detector (the signal of the mass spectrometer being often more variable in time and less reproducible than that provided by the PID detector) for a known amount of tar introduced i.
- the PID detectors 26 and 32 are calibrated using standard atmospheres of increasing tar concentration i, generated by the tarmac atmosphere generator 28.
- concentration of tars of said atmospheres being known, it is necessary to raise the detector response
- PID signal (26) (i) represents the signal of PID 26 or 32 given in isobutylene equivalent.
- the unit of the response coefficient CF PID (i) is mg.Nm ⁇ 3 / ppb v .
- the coefficients CF PID (i) depend on:
- the power of the lamp for example 10.6 eV
- water content which can affect the value of the CF PID response coefficient (i) by more than 30% when the relative humidity of the gas to be analyzed increases from 0 to 100%.
- the response coefficient of the PID CF PID (i) is small, then the PID has a high measurement sensitivity for the tar i and conversely if CF PID (i) is large, then the sensitivity of the PID detector relative to the tar i is weak. It should be noted that the response coefficients CF PID (26) (i) and CF PID (32) (i) for a The same tar may be different in that the temperature and pressure conditions in which the measurements are made may differ from one PID detector to another. We will now describe the calibration procedure of the set ⁇ GC / PID (26) ⁇ which can be done in several ways.
- a first way is to inject directly via the line BIl and the multi-channel valve 20 an atmosphere of known concentration in tar i in the column 21 and to raise the signal provided by the PID detector 26 GC / PID signal (26) (i) given for example, isobutylene equivalent. It is then necessary to calculate for each tar i by linear regression (2 points of minimum measurement) the following coefficient of response:
- GC / PID Signal (26) (i) represents the subset signal ⁇ GC + PID (26) ⁇ given in isobutylene equivalent.
- the unit of CF GC / PID (26) (i) is mg / ppb v .
- Another way to calibrate the set ⁇ GC / PID (26) ⁇ is to introduce a micro-syringe containing a mass m mjecté (i) known tar i in the injector 24 and then raise the signal delivered by the PID detector 26 and this for different masses injected (i) • The linear response is then determined by linear regression for each tar i It should be noted that it is possible to gain in calibration time to inject an atmosphere of n tars i whose composition and total concentration are known in order to proceed to the simultaneous determination of several response coefficients using the law. following mixtures:
- the calibration of the SPME fiber consists of determining the partition coefficients K (i) between the SPME fiber 13 and each tar i present in the gas matrix to be sampled.
- K (i) dimensionless dimension is defined at equilibrium by the following formula: CJ ⁇ re where (i) represents the concentration of tar i on the SPME fiber 13 at equilibrium and C TM mpoule (I) represents the concentration of tar in the i sampling ampoule 12 at equilibrium.
- a first method consists in using the previously determined CF GC / PID response coefficients (26) (i) so that, from the introduction of an atmosphere of n tars, the concentrations C i m p (i) generated by the tar atmosphere generator device 28 are known, it is possible to calculate at equilibrium the concentration of tar i on the fiber SPME CJ ⁇ re (i), expressed in mg.Nm 3 , from the following formula:
- K (i) of a SPME fiber in PDMS for a given class of species, for example the n-alkanes
- LTPRI Linear Temperature -Programmed Retention Index
- the stationary phase is chosen to be identical to that of the SPME fibers 13.
- the injection temperature in the injector 24 is chosen slightly below the temperature limit of resistance.
- temperature of the SPME 13 fiber in order to have a desorption that is as fast as possible so as to have chromatographic peaks of optimal quality. It is then a matter of optimizing the thermal program to be imposed on the oven of the capillary columns 21 and 25 as well as the flow of vector gas 19.
- an atmosphere of known concentration is injected.
- the operating conditions of SPME sampling that are the pressure and the temperature are two parameters which must be optimized in order to have an extraction of tars present in the gaseous state which is sufficient in terms of quantity and fast enough, that is to say that is, the equilibrium time must be less than 5 minutes.
- the temperature is determined so as to have a good compromise between a good sensitivity of the measurement (depending on the mass of absorbed compounds at equilibrium m ⁇ flbre) and a relatively low sampling time (less than 5 min).
- T 2 T 3 > T 2 > Ti
- a pressure SPME extraction is recommended because it is particularly advantageous for the measurement of traces of tars. Indeed, for a given volume, the amount of tar adsorbed on the SPME fiber 13 increases with the pressure within a certain given range. However, the value of the pressure is limited by the tars condensation phenomenon that occurs when the partial pressure of a tar i becomes greater than its saturation vapor pressure. A pressure measurement thus makes it possible to have a sufficient SPME extraction sensitivity and thus to increase the temperature, which will prevent certain tars from condensing and thereby reducing the time to reach equilibrium. Furthermore, the gas to be characterized is under pressure in the main pipe P, which makes it possible to approach actual measurement conditions.
- the sampling of the invention has the particularity of being double and thus imposing the respect of compromises, and first of all a sharing of tars between the fiber 13 and the bulb 12: the fiber 13 is used for separate sampling of the different species of tars, and the content of the bulb 12 for an overall sampling of the gas. Even if condensation of the tars in FIG. 13 is required, it must not excessively deplete the contents of the bulb 12. It is also to obtain satisfactory overall sampling that it can avoid condensations on the bulb 12, which makes relatively high temperatures and fibers 13 resistant to such temperatures preferable.
- the maximum temperature in the sampling bulb 12 making it possible to reach a detection threshold close to 0.1 mg.Nm -3 for most species by chromatography coupled to a flame ionization detector is 80 0 C ( Figure 5).
- the detection limit for naphthalene at the temperature of 80 0 C and at the pressure of one bar is 80 ⁇ g.m "3.
- the previous detection threshold was determined by taking the following criterion:
- This criterion was chosen because the criterion usually taken into account for the determination of the detection thresholds (signal-to-noise ratio of 2) does not allow to have a quantitative measurement in the sense that the maximum error committed can be 50%. .
- the data processing system 36 comprises a processor and one or more databases dedicated inter alia to the recognition of the spectra.
- the values of the response coefficients previously explained are not available, it is necessary to determine the tars i whose response coefficients must be calculated in priority.
- measurements are taken at line B2 and by means of the PID detector 26 synchronized to the mass spectrometer 27, the tar whose Signal Signal S ° PME / GC / PID (26) (i) is maximum.
- This tar is defined as tar 1.
- an ordered sequence of n tars is defined such that the sum of their signals is equal to 90% (this threshold is not imperative) of the sum of the total signals delivered. by the PID detector 26.
- the subset of data processing and calibration gives the device a real autonomy that allows to enrich the database.
- All ⁇ t, n Signal sPME / GC / PID signals (26) (i) are emitted by the set ⁇ SPME / GC / PID ⁇ .
- Each Signar signal sPMEIGCIPIDi26 ) (i) is multiplied by the response coefficient of the set GC GC / PID (26) (i), which gives the value of the mass of tar absorbed i SPME fiber 13 at equilibrium TM ⁇ re m (i).
- the latter is proportional to the concentration CJ ⁇ re (i) of the tar i at the surface of the fiber at equilibrium (b and a are the outer radius and the inner radius of the absorbent part of the fiber, and L flbre its length ).
- the set of C oampoule (i) will be summed to calculate the mass fractions x m (i) and molar x n (i) of each tar i (see Equations (1) and (2) of Figure 3 ) which make it possible to calculate the quantity which interests us, that is to say the overall correction coefficient of the PID 32 CF m ⁇ xPID (32) which also makes use of the different coefficients of response CF PID (32) (i) tars i PID detector 32.
- the continuous signal Signal ° otPID (32) is multiplied by the coefficient CF maPID (32) , the latter is considered constant during ⁇ t.
- the value obtained Signal ° ot PID (32) x CF m ⁇ x PID (32) is a continuous value of the total concentration of tars which is representative of that prevailing in the main pipe provided that the inequality (4) ( Figure 3 following is verified:
- the above inequality can be checked at variable intervals according to the necessity of the measurement.
- Some compounds other than tars contribute significantly to the response of the PID detector 32; - Some tars i are not detectable by the PID detector.
- the response coefficients determined by the measurement line B1 provide information on the limitations of the different materials and parameters used.
- the measurement line B1 makes it possible to verify that all the tars detected by the mass spectrometer 27 are well measurable by the PID detector 26.
- the compounds contributing significantly to the response of the PID detector 26 and which are not tars are identified by the Synchronized indication of the mass spectrometer 27.
- This is information on the limitations of the invention which may lead to the use of a filter medium to absorb these compounds which would have a significant contribution to the overall signal provided by Another means would be to perform a comparative measurement at the level of the measurement line B2 by replacing the filtering medium 30 with a catalytic bed enabling continuous cracking of the tars. It would then be necessary to add a PID detector in parallel to the PID detector 32 to compare the signal from the cracked stream to that of the uncracked stream.
- the various components of the tar measuring device are sized according to the volume flow rates of gas ⁇ p flowing in the main pipe and pressure and temperature conditions, respectively P p and T p , prevailing in the latter.
- Targeted measurement range 0.1 to 50 mg.Nm "3 - Filter medium material 4: fiberglass
- Effectiveness of the frit 5 99.9% for a particle diameter greater than 2 microns.
- Holding temperature of the frit 5 400 0 C - Holding temperature of the pipes and other elements upstream of the measuring lines B1 and B2: 400 ° C.
- Diameter of connecting ducts 1/8 inch or 3 mm; - Sample gas flow ⁇ d2 : 0.7 Nm 3 / h
- volume of the sampling bulb 12 20 L
- Injector type 24 Classic liner - Injection temperature 24: 270 0 C Injection time 24: ⁇ 30 s Diameter of capillary columns 21 and 25: 0.2 mm Length of capillary columns 21 and 25: 10 m - Material of the stationary phase of columns 21 and 25: PDMS
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FR0656004A FR2910966B1 (fr) | 2006-12-28 | 2006-12-28 | Dispositif de mesures couplees permettant un suivi global et en continu de traces de goudrons presentes dans un flux gazeux |
PCT/EP2007/064639 WO2008080987A1 (fr) | 2006-12-28 | 2007-12-28 | Dispositif et procede de mesures couplees permettant un suivi global et en continu de traces de goudrons presentes dans un flux gazeux |
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EP07858227A Withdrawn EP2106549A1 (fr) | 2006-12-28 | 2007-12-28 | Dispositif et procede de mesures couplees permettant un suivi global et en continu de traces de goudrons presentes dans un flux gazeux |
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US (1) | US8054082B2 (ja) |
EP (1) | EP2106549A1 (ja) |
JP (1) | JP2010515040A (ja) |
CN (1) | CN101583869A (ja) |
BR (1) | BRPI0721109A2 (ja) |
CA (1) | CA2672272A1 (ja) |
FR (1) | FR2910966B1 (ja) |
WO (1) | WO2008080987A1 (ja) |
ZA (1) | ZA200903675B (ja) |
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DE102009004278A1 (de) * | 2009-01-05 | 2010-07-15 | Synthesechemie Dr. Penth Gmbh | Messgerät für geringe Kohlenwasserstoffkonzentrationen |
US9075016B2 (en) | 2009-12-31 | 2015-07-07 | Emilcott Associates, Inc. | Automated control of analytical sampling with environmental monitoring system |
US8584509B2 (en) | 2009-12-31 | 2013-11-19 | Emilcott Associates, Inc. | Environmental monitoring system and method with a prefilter |
FR2970077B1 (fr) * | 2010-12-31 | 2014-09-26 | Total Raffinage Marketing | Analyse de fluide circulant dans un conduit |
EP2682744A4 (en) * | 2011-03-02 | 2014-10-15 | Horiba Stec Co Ltd | DATA PROCESSING DEVICE FOR A GAS CHROMATOGRAPH AND DATA PROCESSING PROGRAM USED THEREOF |
KR101243883B1 (ko) | 2011-10-05 | 2013-03-20 | 대한민국(국가기록원) | 유기질 문화재의 비파괴 동정방법 및 이를 이용한 유기질 문화재의 복원 방법 |
EP2642289A1 (en) | 2012-03-20 | 2013-09-25 | Sensirion AG | Portable electronic device |
US9772317B2 (en) * | 2012-07-26 | 2017-09-26 | Sensirion Ag | Method for operating a portable electronic device |
CN103063596A (zh) * | 2012-12-31 | 2013-04-24 | 攀钢集团西昌钢钒有限公司 | 一种检测低焦油焦炉煤气中的焦油含量的方法 |
US20140260694A1 (en) * | 2013-03-15 | 2014-09-18 | Chevron U.S.A. Inc. | Automated Tracer Sampling and Measurement System |
WO2014148981A1 (en) * | 2013-03-19 | 2014-09-25 | Verdant Chemical Technologies | Process and system for controlled tar cracking or tar reforming using a photo ionization detector |
AU2015231494A1 (en) * | 2014-03-17 | 2016-09-01 | MLS ACQ, Inc. D/B/A MAX Analyical Technologies | Process and system for rapid sample analysis |
TWI739300B (zh) | 2015-01-15 | 2021-09-11 | 美商Mks儀器公司 | 離子化計及其製造方法 |
JP6810649B2 (ja) * | 2016-05-17 | 2021-01-06 | 株式会社堀場製作所 | ガス分析装置 |
CN107328760B (zh) * | 2017-06-07 | 2020-09-25 | 长春工业大学 | 一种针对合金样品表面蒸汽对lips测量改进的方法 |
JP6811146B2 (ja) * | 2017-06-23 | 2021-01-13 | 東京エレクトロン株式会社 | ガス供給系を検査する方法 |
CN108709945B (zh) * | 2018-05-25 | 2021-04-13 | 浙江省环境监测中心 | 一种VOCs固定源在线监测监控方法 |
CN108413994B (zh) * | 2018-05-25 | 2024-05-03 | 陕西哲晟电力工程有限公司 | 一种电力光纤传感装置 |
CN108548701A (zh) * | 2018-06-12 | 2018-09-18 | 北京首仪华强电子设备有限公司 | 一种用于取气的装置 |
DE102018126467A1 (de) * | 2018-10-24 | 2020-04-30 | Hochschule Karlsruhe-Technik Und Wirtschaft | Verfahren und Messsystem zur Erfassung eines Teergehalts in Gasen |
KR102691306B1 (ko) * | 2018-11-13 | 2024-08-05 | 삼성전기주식회사 | 적층 세라믹 전자부품 |
CN109374793A (zh) * | 2018-12-20 | 2019-02-22 | 北京市环境保护科学研究院 | 一种测定实际土壤中芳香烃的有机碳-水分配系数的方法 |
US20210010983A1 (en) * | 2019-07-09 | 2021-01-14 | Nanova Environmental, Inc. | Microchannel photoionization detector |
CN111830192B (zh) * | 2020-06-02 | 2022-05-31 | 合肥通用机械研究院有限公司 | 一种混空燃气燃烧性能测试系统及其测试方法 |
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RU2074389C1 (ru) | 1990-10-22 | 1997-02-27 | Марин Шейл Проусессорз Инк. | Способ непрерывного контроля потока, состоящего из смеси пара, дисперсных частиц и газов, потенциально содержащих хлористый водород, и проходящего в вытяжных трубах, и система для его осуществления |
NO175834C (no) * | 1992-09-02 | 1994-12-14 | Norsk Hydro As | Utstyr for prövetakning og opparbeiding til analyse av PAH og andre organiske forbindelser, samt hydrogenfluorid og svoveloksider |
US5703360A (en) * | 1996-08-30 | 1997-12-30 | Hewlett-Packard Company | Automated calibrant system for use in a liquid separation/mass spectrometry apparatus |
DE19832411C2 (de) | 1997-09-15 | 2001-10-18 | Oliver Moersch | Anordnung zur Messung des Gehalts an kondensierbaren Kohlenwasserstoffen in kohlenwasserstoffhaltigen Gasen |
US6225633B1 (en) * | 1998-10-22 | 2001-05-01 | Rae Systems, Inc. | Photo-ionization detector for volatile gas measurement and a method for self-cleaning the same |
JP3876554B2 (ja) * | 1998-11-25 | 2007-01-31 | 株式会社日立製作所 | 化学物質のモニタ方法及びモニタ装置並びにそれを用いた燃焼炉 |
JP4105348B2 (ja) * | 1999-11-19 | 2008-06-25 | 株式会社日立製作所 | 試料分析用モニタ装置及びそれを用いた燃焼制御システム |
FR2834052B1 (fr) | 2001-12-20 | 2004-03-19 | Snecma Moteurs | Procede pour le suivi du deroulement d'un processus utilisant un gaz reactif contenant un ou plusieurs hydrocarbures gazeux |
JP2005274502A (ja) | 2004-03-26 | 2005-10-06 | Matsushita Electric Ind Co Ltd | 捕捉材における捕捉量の評価方法 |
US20080260587A1 (en) * | 2004-07-02 | 2008-10-23 | Dennis Coleman | Hydrocarbon Preparation System |
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2006
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2007
- 2007-12-28 EP EP07858227A patent/EP2106549A1/fr not_active Withdrawn
- 2007-12-28 US US12/518,505 patent/US8054082B2/en not_active Expired - Fee Related
- 2007-12-28 BR BRPI0721109-0A patent/BRPI0721109A2/pt not_active IP Right Cessation
- 2007-12-28 CN CNA200780047192XA patent/CN101583869A/zh active Pending
- 2007-12-28 CA CA002672272A patent/CA2672272A1/fr not_active Abandoned
- 2007-12-28 JP JP2009543482A patent/JP2010515040A/ja active Pending
- 2007-12-28 WO PCT/EP2007/064639 patent/WO2008080987A1/fr active Application Filing
-
2009
- 2009-05-27 ZA ZA200903675A patent/ZA200903675B/xx unknown
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US20100045300A1 (en) | 2010-02-25 |
BRPI0721109A2 (pt) | 2014-03-04 |
CN101583869A (zh) | 2009-11-18 |
ZA200903675B (en) | 2010-04-28 |
WO2008080987A1 (fr) | 2008-07-10 |
CA2672272A1 (fr) | 2008-07-10 |
US8054082B2 (en) | 2011-11-08 |
JP2010515040A (ja) | 2010-05-06 |
FR2910966A1 (fr) | 2008-07-04 |
FR2910966B1 (fr) | 2009-04-17 |
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