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    • 专利摘要:
    The invention relates to a method and system for in situ measurement of the concentration of gaseous chemical species, such as NO, NO2, NH3, BTX, SO2, H2S, O3, O2 contained in exhaust gases (10). circulating in an exhaust line (20) and the temperature of said gases by means of an optical measuring system comprising a light source (41) and a spectrometer (44). The source emits UV radiation through the gases within a measurement zone (21) located in the line. The spectrometer detects at least a portion of said UV radiation having passed through the gas and generates a digital signal of the light intensity (50) as a function of the wavelength of the portion of the UV radiation having passed through the gases. The concentration of the chemical species and the temperature of the gases is then estimated from the digital signal.
    公开号:FR3069641A1
    申请号:FR1757140
    申请日:2017-07-27
    公开日:2019-02-01
    发明作者:Matthieu Lecompte；Philpp Schiffmann；Olivier Laget；Pascal Hayrault
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    Field of the invention
    The present invention relates to the measurement of the concentration of chemical species contained in exhaust gases and of the temperature of such gases, preferably originating from an internal combustion engine, by means of an optical system.
    The present invention advantageously applies to the field of pollution control of exhaust gases and monitoring of pollutant emissions of exhaust gases.
    General context
    The emission standards for pollutants from combustion in heat engines now require, in most cases, the reduction of the concentrations of these substances, for example by means of post-combustion catalytic treatments.
    The pollutants in the exhaust gases are conventionally unburnt hydrocarbons, carbon monoxide (CO), nitrogen monoxide (NO) and nitrogen dioxide (NO 2 ) commonly known by the acronym NO X , nitrous oxide N 2 O, ammonia (NH 3 ), sulfur compounds such as hydrogen sulfide (H 2 S) or sulfur oxides such as sulfur dioxide (SO 2 ), ozone O 3 , etc. Some of these substances are subject to strict regulations, according to which limit concentrations must be observed when discharged into the atmosphere. NOx, for example, has a harmful impact directly on human health and indirectly through the secondary formation of tropospheric ozone. The regulations already impose a control of the concentration of the NOx group formed by these nitrogen oxides, and may have to evolve to impose control of each nitrogen oxide individually, for example NO 2 . Regarding NOx, it is known to use a selective catalytic reduction system (SCR) on the exhaust gas line which allows nitrogen NOx to be selectively reduced by the action of a reducing agent generally injected upstream of the SCR system, for example ammonia or a compound generating ammonia by decomposition, such as urea. Thus, ammonia also represents a substance for which concentration monitoring can be useful, not only in the context of concentration control imposed by current or future standards, but also for the purpose of diagnosis and / or of the pollution control system.
    In this context, it is advantageous to be able to measure the concentration of polluting substances, in particular in order to control and / or diagnose the post-combustion depollution systems.
    The development of sensors and methods adapted to the measurement of each polluting substance is therefore of major interest.
    It is known systems for quantifying ammonia, and other chemical compounds contained in exhaust gases, by using a light source emitting in the Infra-Red (IR) or the Ultraviolet (UV) .
    Patent application US2013 / 0045541 describes for example a sensor and a method for determining the concentration of one or more gaseous species in exhaust gases of an internal combustion engine, based on an optical measurement and implementing an IR or UV light source. According to this prior art, the chemical species whose concentration it is desired to determine are transformed in a catalytic chamber into secondary chemical species which interact, by absorption or diffusion, with IR or UV light. Spectral analysis of the light having passed through these secondary chemical species then makes it possible to estimate the concentration of the initial gaseous species. Thus the estimation of the ammonia concentration can be carried out indirectly by the measurement of nitrogen oxides resulting from the catalytic transformation of ammonia. A drawback of this method consists in the need to transform the chemical species via a catalytic chamber in order to have access to their concentration, providing an indirect measurement less precise than a direct measurement, and requiring bulky and complex analysis equipment which must integrate a catalytic chamber. Furthermore, it is not possible, according to this method, to carry out a dissociated measurement of the concentration of nitrogen oxides NO and NO 2 .
    Another method is known, described in patent EP0107535, which evokes the principle of absorption of UV radiation by certain compounds of exhaust gas and the use of this principle to regulate the combustion of a heat engine, and in particular to evaluate the power supply of the engine. According to this method, a tracer of the quality of combustion is detected by optical measurement. This tracer consists of compounds added to the fuel or to the combustion air, before entering the combustion chamber. These compounds are compounds normally destroyed by combustion, for example aromatic compounds such as benzene or toluene, or compounds which react more or less in connection with the quality of combustion by providing at least one product which absorbs UV radiation. However, this method is limited to the detection of the richness of the combustion gases, and involves the addition of specific compounds to the exhaust gases, which may be undesirable with a view to cleaning up the exhaust gases. In addition, EP0107535 does not describe any optical measurement of the concentration of polluting substances in exhaust gases such as NOx or sulfur compounds such as H 2 S or sulfur oxides.
    There are also commercially available optical sensors that can be used for gas analysis. However, most of these sensors are either bulky, not allowing an in situ measurement in vehicle exhaust lines, or they do not provide a measurement but are probes sensitive to the presence of certain gaseous chemical species, or require a gas sampling system making the device complex and the measurement less reliable.
    In addition, another type of information is of major importance in the field of exhaust gas pollution control: the temperature of the exhaust gases. Knowledge of the temperature of the exhaust gases, simultaneously with that of the concentrations of polluting substances, provides access to an additional level of information that is extremely useful for checking and / or diagnosing post-combustion depollution systems. However, access to temperature information is conventionally carried out using a dedicated sensor (thermocouple), which adds to the complexity of the implementation of the measurement.
    Objectives and summary of the invention
    The object of the present invention is to provide an in situ optical measurement of the concentration of gaseous chemical species contained in exhaust gases and of the temperature of such exhaust gases, by means of a single measurement system. optical.
    The present invention also aims to satisfy at least one of the following objectives:
    - solve, at least partially, the problems mentioned above in relation to the known methods and systems for quantifying chemical compounds in exhaust gases;
    - provide a system for optical measurement of the concentration of gaseous chemical species of exhaust gases and of the temperature of said exhaust gases which is compact and which can be carried in a vehicle;
    - allow a dissociated, that is to say individual, measurement of different gaseous chemical species contained in the exhaust gases, for example NO, NO 2 and NH 3 ;
    - allow simultaneous quantification of the concentration of different gaseous chemical species contained in the exhaust gases;
    - allow the diagnosis and / or control of a post-combustion depollution system based on measurements of the temperature of the exhaust gases and the concentration of gaseous chemical species contained in said exhaust gases by means of a one and the same optical measurement system.
    Thus, in order to achieve at least one of the abovementioned objectives, among others, the present invention proposes, according to a first aspect, a method for in situ measurement of the concentration [X] of at least one gaseous chemical species contained in exhaust gas flowing in an exhaust line and the temperature of the exhaust gas by means of an optical measurement system, the optical measurement system comprising at least one light source and a spectrometer, comprising the following steps :
    - the emission by the light source of UV radiation through the exhaust gases within a measurement zone located in the exhaust line;
    the detection by the spectrometer of at least part of the UV radiation having passed through the exhaust gases in the measurement area and the generation of a digital signal of the light intensity as a function of the wavelength W of the part of the UV radiation which has passed through the exhaust gases;
    - the estimate of the concentration [X] of the chemical species and the temperature T of the exhaust gases from said digital signal.
    According to an implementation of the invention, the optical measurement system further comprises a reflector, and the method comprises a step in which the UV radiation emitted by the light source passes through the exhaust gases in the measurement zone for then be reflected by the reflector, crosses again the exhaust gases in the measurement area in the opposite direction to be then detected by the spectrometer.
    According to an implementation of the invention, the method comprises a preliminary step of calibrating the optical measurement system to provide a digital reference signal of the light intensity as a function of the wavelength, preferably by emission of the radiation UV through a reference gas, for example a reference gas containing none of the chemical species to be measured, and by detection of at least part of the UV radiation having passed through the reference gas to provide a digital reference signal of l light intensity as a function of the wavelength of the part of the UV radiation having passed through the reference gas.
    According to an implementation of the invention, the step of estimating the concentration [X] of said chemical species and the temperature T of the exhaust gases comprises:
    the determination of the absorbance A of the exhaust gases as a function of the wavelength from said digital signal of the light intensity as a function of the wavelength of the part of the UV radiation having passed through the gases d 'exhaust and a digital reference signal;
    - Determining the concentration [X] of said at least one chemical species from the absorbance of said exhaust gases and predetermined absorbance, temperature and pressure characteristics of the chemical species;
    the determination of the temperature T of the exhaust gases by modification of the molar extinction coefficient of the absorbance of the chemical species extracted from the absorbance of the exhaust gases, the modification being a shift in the length of wave or a change in amplitude or a combination of both.
    Preferably, the absorbance A of the exhaust gases is a function of the absorbance length, of the number of densities of the molecules of the chemical species and of the molar extinction coefficient.
    According to an implementation of the invention, the UV radiation emitted has a wavelength between 180 and 400 nm, preferably between 180 and 280 nm, and even more preferably between 180 and 240 nm.
    Preferably, the concentration of at least one, and preferably several, gaseous chemical species contained in the exhaust gases, and included in the list constituted by: NO, NO 2 , N 2 O, BTX, SO 2 , is measured. , H 2 S, O 3 , O 2 , H 2 O, aldehydes such as acetaldehyde or formaldehyde, non-aromatic hydrocarbons such as acetylene or buta-1,3-diene.
    According to an implementation of the invention, the concentration of at least two gaseous chemical species is measured simultaneously, and preferably at least the concentration of NO and the concentration of NO 2 .
    This implementation can be applied to the control of NOx at the outlet of a pollution control system, preferably at the outlet of a selective catalytic reduction system, or applied to the control of NOx upstream and downstream of a pollution control system , in which at least the concentration of NO and the concentration of NO 2 are measured, preferably to estimate the real-time conversion of NOx to N 2 by the depollution system.
    According to an implementation of the invention, the concentration of at least one gaseous chemical species chosen from the sulfur-containing chemical species SO 2 and H 2 S is measured, and preferably both.
    According to an implementation of the invention, the concentration of at least NH 3 is measured.
    This implementation can be applied to the control of NH 3 upstream or downstream of a selective catalytic reduction system, in which the evolution of the NH 3 concentration is monitored upstream or downstream of the selective catalytic reduction system. .
    Advantageously, the exhaust gases come from an internal combustion engine.
    According to an implementation of the invention, UV radiation passes through the exhaust gases along an optical path substantially perpendicular to the path P of the exhaust gases.
    According to an implementation of the invention, the in situ measurement is carried out downstream of at least one exhaust gas depollution system such as a diesel oxidation catalyst, a selective catalytic reduction system or a particles.
    According to an implementation of the invention, the in situ measurement is carried out upstream of at least one exhaust gas depollution system such as a diesel oxidation catalyst, a selective catalytic reduction system or a particles.
    According to a second aspect, the present invention provides an optical measurement system for the in situ measurement according to the invention of the concentration [X] of at least one gaseous chemical species contained in exhaust gases flowing in a line of the exhaust gas temperature T, the system comprising:
    a light source capable of emitting UV radiation through the exhaust gases within a measurement zone located in the exhaust line, the light source preferably being positioned so as to emit UV radiation according to a optical path substantially perpendicular to the path P of the exhaust gases;
    - a spectrometer capable of detecting at least part of the UV radiation having passed through the exhaust gases in the measurement area and the generation of a digital signal of the light intensity as a function of the wavelength W of the part UV radiation having passed through the exhaust gases;
    - means of analysis and processing of said signal to determine the concentration [X] of the chemical species and the temperature T of the exhaust gases from said digital signal.
    Other objects and advantages of the invention will appear on reading the following description of examples of particular embodiments of the invention, given by way of nonlimiting examples, the description being given with reference to the appended figures described below. -after.
    Brief description of the figures
    FIG. 1A is a diagram illustrating the optical measurement of the concentration of chemical species contained in exhaust gases and of the temperature of such gases, according to an embodiment of the invention.
    FIG. 1B is a diagram illustrating the optical measurement of the concentration of chemical species contained in exhaust gases and of the temperature of such gases, according to another embodiment of the invention.
    FIG. 2 schematically represents the absorbance of the exhaust gases comprising different gaseous chemical species A, B, C which it is desired to measure.
    FIG. 3 schematically represents the influence of the temperature on the absorbance of a given chemical species contained in the exhaust gases.
    Figures 4 to 14 are diagrams illustrating different implementations of the invention in the context of depollution of exhaust gases.
    In the figures, the same references designate identical or analogous elements.
    Description of the invention
    The object of the invention is to propose a method for in situ measurement of the concentration of at least one gaseous chemical species contained in exhaust gases and of the temperature of such gases circulating in an exhaust line by means an optical measurement system 40.
    Preferably, the exhaust gases come from an internal combustion engine.
    Figures 1A and 1B schematically represent the measuring principle according to the invention. Figure 1A differs from Figure 1B in the optical measurement system, which is in a transmissive configuration in Figure 1A and in a reflective configuration in Figure 1B.
    The present invention allows measurement in situ, that is to say directly in the exhaust line 20 of the gases 10, and without taking a sample of gas or transformation or preconditioning of said gas, typically a transformation of a non-measurable chemical species into other measurable chemical species, for measurement purposes.
    The measurement according to the invention is therefore non-intrusive, and has the advantage of not modifying the flow of the exhaust gases and of being instantaneous, for example with a response time which may be less than 0.1 s, unlike the known methods for sampling gases, in which there is an addition of back pressure, a possible development of the gases to be analyzed during the sampling, which is undesired, and a transit of the gases to the measuring cell causing a delay in measurement.
    The optical measurement system according to the invention, allowing measurement in situ, can thus be easily embarked on a vehicle, or any other mobile device comprising an exhaust line of exhaust gases from an internal combustion engine.
    The optical measurement system comprises at least one light source 41 and a spectrometer 44.
    The measurement process includes the following steps:
    the emission by the light source 41 of UV radiation 42 through the exhaust gases 10 within a measurement zone 21 located in the exhaust line 20. The UV radiation 42 passes through the exhaust gases exhaust, along an optical path, of length d, which can be substantially perpendicular to the path P of the exhaust gases, as shown in FIGS. 1A and 1B. According to an alternative configuration, the optical path can be different, for example substantially tangent or parallel to the path P of the exhaust gases, in the case where the optical system comprises a reflector as shown in FIG. 1B, and is positioned in a specific manner , as described in connection with Figures 13 and 14 below. UV radiation 42 enters the measurement zone located in the exhaust line through an optical access, for example a window or a lens.
    - The detection by the spectrometer 44 of at least part 43 of the UV radiation having passed through the exhaust gases in the measurement zone 21, and the generation of a digital signal 50 of the light intensity as a function of the length of the part of the UV radiation which has passed through the exhaust gases. The gaseous chemical species whose concentration is to be measured absorb part of the UV radiation and each gaseous chemical species absorbs the rays at certain given wavelengths. The absorption follows, under ideal conditions, the Beer-Lambert law. UV radiation having passed through the exhaust gases is detected by the spectrometer 44 through another optical access, as for emission by the light source.
    - the estimate of the concentration [X] of the gaseous chemical species and of the temperature T of the exhaust gases 10 from the digital signal 50.
    While the pattern is transmissive in the embodiment shown in Figure 1A, the pattern is reflective in the embodiment shown in Figure 1B. According to this reflective configuration, the optical system 40 further comprises a reflector 45. The UV radiation emitted by the source 41 is reflected by the reflector 45, positioned at the end of the measurement zone 21 opposite the end where there are the light source 41 and the spectrometer 44. The reflector 45 is preferably positioned in the exhaust line 20, as illustrated in FIG. 1 B. It can alternatively be integrated into the wall of the exhaust line, or be arranged outside of it. The UV radiation 42 passes through the exhaust gases 10 for the first time in the measurement zone 21, is reflected by the reflector 45, passes through the exhaust gases a second time in the opposite direction in the measurement zone 21, and is then detected by spectrometer 44, as described above.
    Whether in the case of a transmissive or reflective configuration, the light source 41 and the spectrometer 44 are preferably positioned outside the exhaust line, for example on the external face of the walls of the line, or away from the line if means for transmitting radiation are provided, such as for example optical fibers as shown in FIGS. 10 and 11 and described below. This in particular makes it possible to avoid damage to these optical elements due to the high temperatures which may be encountered in the exhaust gases.
    The method according to the invention preferably comprises a preliminary step of calibrating the optical measurement system making it possible to obtain a digital reference signal of the light intensity as a function of the wavelength. Preferably, this step consists in emitting UV radiation through a reference gas, for example a gas containing none of the chemical species to be measured, such as helium, dinitrogen or air, or through a gas of reference which contains certain chemical species which one wishes to measure and of which one knows the concentration in said gas. The radiation passes through the reference gas, and is then detected by the spectrometer to provide a digital reference signal of the light intensity as a function of the wavelength of the part of the UV radiation which has passed through the reference gas. The reference signal is used in the concentration and temperature estimation step, in particular to calculate the absorbance of the exhaust gases, as described in detail below.
    By exhaust gas is meant the exhaust gases from an internal combustion engine, in particular, but not exclusively, for a motor vehicle. However, this does not in any way rule out all other types of exhaust gas resulting from combustion, such as those from boilers or ovens, and circulating in a chimney or an exhaust duct that can integrate the optical measurement system. described here. The present invention can thus be applied to industrial fumes for which it is desired to measure the temperature and the concentration of certain chemical species in gaseous form.
    The UV radiation emitted by the light source 42 has a wavelength between 180 and 400 nm, preferably between 180 and 280 nm, and more preferably between 180 and 240 nm. This wavelength range is part of what is called deep UV.
    For example, the light source can be a LED diode emitting in the UV and in particular in the deep UV as indicated above, or perhaps a xenon, deuterium, zinc lamp, cadmium, or another gas lamp like KrBr, KrCL, KrF excimer lamps.
    The spectrometer makes it possible to analyze the light signal in the wavelength range 180-400 nm, preferably 180-280 nm, and more preferably 180-240 nm. Alternatively, a simplified system for analyzing a reduced wavelength range can be used. The term spectrometer is retained in the present invention to designate such a simplified system.
    The assembly formed by the UV light source and the spectrometer, also called optical sensor in the present invention, is known per se. Such optical sensors can be found commercially.
    The optical sensor may include other elements, in particular optical elements such as lenses making it possible to modify the light beam if necessary (for example convergence or divergence), or even protective elements intended to protect the light source and the spectrometer, especially during cold operation of the optical measurement system. Indeed, cold operation can cause deposits on the optical elements by a phenomenon of condensation. Such protective elements are described below, in relation to FIG. 12. The position of the sensor installed on the exhaust line can be chosen so as to limit the fouling thereof. For example, the sensor can be positioned at the outlet of a particle filter (FAP) in the case where the exhaust line includes such a FAP.
    According to the invention, it is possible to carry out the measurement of at least one gaseous chemical species X, and preferably several gaseous chemical species X, included in the list constituted in a nonlimiting manner by: NO, NO 2 , N 2 O, NH 3 , BTX, SO 2 , H 2 S, O 3 , O 2 , H 2 O, aldehydes such as acetaldehyde or formaldehyde, non-aromatic hydrocarbons such as acetylene or buta-1,3-diene.
    Preferably, the measurement is made of at least one, and more preferably of several, gaseous chemical species included in the list constituted by: NO, NO 2 , N 2 O, NH 3 , BTX, SO 2 , H 2 S, O 3 , O 2 , H 2 O.
    The acronym BTX refers to benzene, toluene and xylenes belonging to the family of aromatic hydrocarbons.
    Advantageously, the dissociated and simultaneous measurement of the concentration of a plurality of these gaseous chemical species can be carried out.
    By dissociated measurement, one understands an access to the own concentration of each chemical species, as opposed to a global measurement of the concentration of several chemical species without distinction, as it can be the case of NOx in certain known methods.
    For example, according to the invention, the concentration of at least two gaseous chemical species is measured simultaneously, preferably at least the concentration of NO and the concentration of NO 2 .
    Nitrogen oxides NO and NO 2 represent regulated air pollutants, which it is advantageous to measure.
    Such a measurement thus allows a control of the NOx at the outlet of a post-combustion depollution system, preferably at the outlet of an SCR system, or a control of the NOx upstream and downstream of a depollution system, preferably d 'an SCR system, to estimate for example the real-time conversion of NOx to N 2 by said depollution system, and while controlling the supply of NH3.
    The SCR system makes it possible to selectively reduce NOx by a reducing agent on a dedicated catalyst. The reduction is said to be selective because the reducing agent reduces the NOx and not the oxygen present in the mixture to be burned. Thanks to such a depollution system, the NOx are converted into dinitrogen N 2 . This reducing agent, in particular for use with an internal combustion engine of a motor vehicle, is either ammonia (or a material which can decompose into ammonia), or an oxygenated or non-oxygenated hydrocarbon, or a mixture of hydrocarbons which may contain in part or in whole one or more oxygenated hydrocarbons. In the case of an exhaust gas treatment with a SCR with ammonia for example, the ammoniacal agent used is stored either in the form of solid complexes, or in the form of a liquid precursor, such as urea in solution aqueous.
    The measurement of NO and NO 2 thus makes it possible to control the NOx upstream and downstream of an SCR system using an ammoniacal agent, to estimate for example the real-time conversion of NOx to N 2 by said depollution system while controlling the contribution of NH 3 .
    Thanks to a measurement of NO dissociated from that of NO 2 , it is possible to know the molar ratio NO / NO 2 composing the NOx.
    It is interesting to know the NO / NO 2 ratio because the NOx reduction reaction with ammonia is different depending on this ratio (faster when NO and NO 2 are in equivalent quantities). In addition NO 2 is useful to help the oxidation of soot present in a FAP for example.
    Thus, if the optical measurement system comprises two optical sensors respectively placed upstream and downstream of the NOx depollution system, it is then possible to know the conversion in real time of NOx to N 2 . An on-board electronic diagnostic system (OBD for On-Board Diagnostics according to English terminology) including the diagnosis of NO 2 is then possible, such a diagnosis may be required in the future by the regulations on polluting emissions from internal combustion engines of rolling vehicles.
    According to the invention, it is also possible to measure the concentration of at least SO 2 , or H 2 S, and preferably at least both. The quantification of the sulfur elements makes it possible, for example, to diagnose a possible poisoning of a post-combustion depollution system which may be linked to the use of fuels with a high sulfur content, or to control the emissions of ships operating in the area. controlled sulfur emission (SECA).
    Advantageously, the concentration of at least NH 3 is measured. In this case, it is possible to monitor the evolution of the NH 3 concentration upstream and / or downstream of the SCR system, in particular in order to control the NH 3 concentration upstream of an SCR system, for example by adjusting the injection of an ammoniacal agent in the SCR system, or to manage the problems of unwanted emission of NH 3 during operation with an SCR system. An ODB including the diagnosis of NH 3 is then possible, such a diagnosis may be required in the future by the regulations on polluting emissions from internal combustion engines of rolling vehicles.
    In the method according to the invention, the concentration of each chemical species is determined from the optical measurement carried out on the exhaust gases and from the optical signature specific to each chemical species. Each gaseous chemical species whose concentration we want to measure indeed absorbs part of the UV radiation and has its own absorption spectrum (absorbance as a function of wavelength).
    During the step of estimating the concentration [X] of at least one chemical species and the temperature T of the exhaust gases, the operations a), b) and c) described below are carried out.
    a) the absorbance A of the exhaust gases is determined as a function of the wavelength W from the digital signal of the light intensity 50 generated by the spectrometer and resulting from the detection of the part of the UV radiation having passed through exhaust gases, and from a digital reference signal. The digital reference signal is preferably established during the preliminary calibration step described above.
    In particular, the absorbance of exhaust gases is calculated according to formula (I) below:
    Absorbance = _ ln (^ 's ^^ appemenA (|) 5ignal r ^ f ^ rence j
    b) The concentration [X] of each chemical species that one wishes to measure is determined, using analysis and signal processing means such as a microprocessor, from the absorbance A of the gases exhaust and predetermined absorbance, temperature and pressure characteristics of each of the chemical species. These predetermined absorbance, temperature and pressure characteristics of each of the chemical species are preferably obtained during prior measurement campaigns making it possible to create a library. Data from the literature can also feed such a library. By absorbance characteristic of a given chemical species is meant its molar extinction coefficient.
    FIG. 2 schematically represents the absorbance A of the exhaust gases comprising different gaseous chemical species A, B, C which it is desired to measure. The diagram on the left represents an example of absorbance A (without unit) of the exhaust gases, expressed as a function of the wavelength W (in nm), calculated from the digital signal of the light intensity 50 generated by the spectrometer and the digital reference signal.
    The absorbance A of the exhaust gases is a function of the absorbance length, i.e. the length of the optical path traversed by the light in the measurement zone located in the exhaust line, of the numerical density of the molecules of gaseous chemical species (A, B, C) contained in the gases, and of the molar extinction coefficient. The molar extinction coefficient, also called molar absorptivity, is a measure of the probability that a photon will interact with an atom or molecule.
    The numerical density of molecules of a chemical species is itself a function of the temperature, pressure and concentration of the chemical species, and the molar extinction coefficient is a function of wavelength, l chemical species, temperature and pressure.
    Thus, by having the predetermined characteristics of the molar extinction coefficient, of temperature and of pressure of each of the chemical species, it is possible to determine the concentration [X] of each chemical species X from the absorbance A of the gases d 'exhaust. The absorbance values of each chemical species add up, and their sum is typically equal to the absorbance A values of exhaust gases, noise and absorbance of other chemical species not measured by. This is represented on the right in FIG. 2 by the absorbance diagrams AA, AB, and AC of the chemical species A, B and C, which add up to form the absorbance A of the exhaust gases, noise and other chemical species not detected by AD.
    Different types of algorithms can be used for concentration calculations, such as least squares adjustment algorithms applied to the absorbance signals themselves, derivatives of the absorbance signals or the frequency part of the d signals. 'absorbance (typically derived from a Fourier transform). Similarly, a number of chemometric methods can be used for this process such as, for example, principal component analysis (PCA) or partial least square algorithms (PLS).
    c) The temperature T of the exhaust gases is determined by modifying the molar extinction coefficient of the absorbance of a chemical species the concentration of which it is desired to measure, said absorbance of the chemical species being extracted from the absorbance of said exhaust gas. The modification of the molar extinction coefficient can be a shift in the wavelength, leading to absorption at different wavelengths, or a modification of the amplitude of the absorbance at a given wavelength, or a combination of the two. When the exact temperature behavior of a chemical species is known, by means of preliminary measurements or data from the literature, making it possible to create a library, this chemical species can be used as an indicator of temperature. The degree of precision in determining the temperature depends on the sensitivity of the molar extinction coefficient of the chemical species in the measured wavelength range. FIG. 3 illustrates the influence of temperature on the absorbance of a chemical species, here ammonia, used to determine the temperature according to the present invention. The curve A-Tc represents the absorbance of NH 3 for a low temperature, for example 20 ° C, and the curve A-Th represents the absorbance of NH 3 for a high temperature, for example 450 ° C. A modification of the molar extinction coefficient, for example, leads to a shift in the absorption signal. Although the example given concerns ammonia, any other chemical species such as NO, NO 2 , N 2 O, BTX, SO 2 , H 2 S, O 3 , O 2 , H 2 O, aldehydes such as acetaldehyde or formaldehyde, non-aromatic hydrocarbons such as acetylene or buta-1,3-diene, can be used to determine the temperature. The same type of algorithms as those used to determine the concentration of chemical species can be used to determine the temperature.
    Thus, the method and the measuring system according to the invention make it possible to access the temperature of the exhaust gases without additional measuring device, conventionally a thermocouple. The instantaneous measurement of the temperature, which is the result of a specific processing of the UV absorption signal, associated with the measurement of the concentrations of gaseous chemical species contained in the gases, provides a clear advantage in the various control strategies. engine, as well as for online evaluation of the efficiency of pollution control systems, etc.
    Table 1 below, and the diagram on the left in FIG. 2, illustrate an example of measurement carried out according to the invention. The measurement is carried out on a synthetic gas mixture, created from pure gaseous species, the exact concentrations of which are known in each of the gaseous species.
    In Table 1, the actual values, known by the synthesis of the gas mixture with regard to the concentrations and by a thermocouple for the temperature of the gas mixture, are compared with the values obtained by the measurement according to the invention.
    Exhaust gas Actual values Measured values NH 3 [pm] 43 37.8 NO [pm] 226 220 NO 2 [pm] 257 275 SO 2 [pm] 20 19.4 O 2 [%] 5.7 6.9 H 2 O [%] 3.6 3.2 Temperature [° C] 105.7 108.3
    Table 1
    An example of measurement ranges obtained with the method according to the invention for the concentrations of the different chemical species are illustrated in table 2 above.
    The values given in Table 2 are estimates made from the measurement on different gaseous mixtures of given syntheses, at various temperature conditions (at room temperature and at 100 ° C.), with an absorbance path of 11 cm.
    Concentration ranges and accuracy may vary depending on the concentration of gaseous chemical species present in the exhaust gas, temperature, pressure and the material used in the optical measurement system (type of source, spectrometer , other optical elements etc.). The measurement range can be adapted by varying the optical path for all gaseous chemical species. In this case, a shorter optical path extends the measurement range but decreases the sensitivity, while a larger optical path reduces the measurement range but increases the sensitivity.
    Chemical species Max value RMSE Min value NH 3 [pm] 300 3 0 NO [pm] 797 8 0 NO 2 [pm] 2393 24 0 SO 2 [pm] 473 5 0 O 2 [%] 100 3 0 CO 2 [% 1 100 9 0 H 2 O [%] 6 0.06 0 Toluene [pm] 17 0 0 C 4 H 6 [pm] 979 10 0 C 2 H 2 [pm] 8814 88 0
    Table 2
    The invention advantageously applies to the field of exhaust gas pollution control. In this context, the optical measurement system can be positioned at different locations on the exhaust line to perform an in situ concentration and temperature measurement suitable for monitoring pollutant emissions upstream and / or downstream of a system. post-combustion gas depollution.
    According to one embodiment, the measurement is carried out downstream of at least one exhaust gas pollution control system such as a diesel oxidation catalyst (DOC), an SCR system or a FAP. Such an embodiment is shown diagrammatically in FIG. 4. The exhaust gases 10 circulate in the exhaust line 20 along the path P, on which is placed a pollution control system 60, for example a DOC, an SCR system. or a FAP. The pollution control system can also be that of a petrol engine, like a three-way catalyst, another pollution control system conventionally used on my Diesel engines, like a PNA ("partial NOx adsorber" in English) or a NOx trap. ("NOx trap" in English). The pollution control system includes one or more elementary pollution control units, each elementary pollution control unit can be a catalytic bar and / or a filter, catalyzed or not, and modifies the composition or content of the exhaust gases. According to the embodiment shown in FIG. 4, the optical measurement system 40 is placed downstream from the pollution control system 60. The upstream and downstream positions are defined relative to the direction of circulation of the exhaust gases in the line of exhaust. The measurement of the temperature of the exhaust gases and of the concentration of certain chemical species of the exhaust gases downstream of the pollution control system 60 makes it possible to verify compliance with the standards for emissions of pollutants, to monitor their development, and whether necessary to adjust the operation of the depollution system to modify the quantities of these substances emitted.
    According to another one embodiment, represented in FIG. 5, the in situ measurement is carried out in an identical manner to that of the embodiment represented in FIG. 4, except that the optical measurement system includes a reflector 45 for a reflective measurement. The optical measurement system is that described in relation to FIG. 2. The source 41 and the spectrometer 44 are placed on the same side of the exhaust line 20, that is to say at the same end of the zone of measure 21, opposite to that where the reflector 45 is positioned.
    According to another embodiment, the in situ measurement is carried out upstream of at least one exhaust gas depollution system such as the three systems mentioned above (DOC, SCR, FAP). Such an embodiment is shown diagrammatically in FIG. 6, identical to FIG. 4 with the exception of the optical measurement system 40 positioned upstream of the pollution control system 60. Such an embodiment can be useful for obtaining information on temperature and concentration of chemical species in the exhaust gases before entering the depollution system, and to use this information to influence, for example, the functioning of the depollution system 60.
    According to one embodiment, the in situ measurement is carried out upstream and downstream of at least one exhaust gas depollution system such as the three systems mentioned above (DOC, SCR, FAP). An example according to this mode is illustrated in FIG. 7, in which two optical measurement systems 40 and 40 'are placed respectively upstream and downstream of a pollution control system 60. The second optical measurement system 40' is identical to the first optical measurement system 40 disposed upstream, and comprises a light source 40 ′ and a light analyzer 44 ′ allowing respectively the emission of UV radiation and the detection and analysis of the UV radiation having passed through the exhaust gases in the measurement zone 21 'located on the exhaust line 20, in order to provide an estimate of the concentration of gaseous chemical species and of the temperature of the exhaust gases. Another example according to this mode is illustrated in FIG. 7, in which the exhaust line comprises two pollution control systems 60 and 61, and three optical measurement systems 40, 40 ', and 40 ”, placed respectively upstream of the first depollution system 60, between the depollution systems 60 and 61, and downstream of the depollution system 61. Such an embodiment also makes it possible to know the efficiency of each depollution system on the exhaust line, and possibly adjust the depollution systems as a function of the concentration and temperature information obtained upstream, downstream and between the depollution systems, in order to control the polluting emissions at the outlet of the exhaust line.
    According to one embodiment, the UV light source and / or the spectrometer of the optical measurement system is connected to the exhaust line by an optical fiber, allowing more flexibility in integrating the optical measurement system with the line exhaust system, in particular as part of a system on board a vehicle. An example of such an embodiment is shown in FIG. 9, where optical fibers 75 and 76 respectively connect the light source 71 and the spectrometer 74 of the optical measurement system 70 to the exhaust line 20, at the level of the measurement zone 21 where the exhaust gases are traversed by the UV radiation conducted by the optical fibers 75 and 76.
    For each of the embodiments shown in FIGS. 5 to 9, the optical system can be that described in relation to FIG. 2, comprising a reflector 45.
    According to one embodiment, the optical measurement system comprises several measurement zones connected to a single light source and a single spectrometer, by means of optical fibers. Such an embodiment makes it possible, for example, to reduce the cost of implementing the optical measurement in the case where measurements upstream and downstream of pollution control systems are desired. An example of such an embodiment is illustrated in FIG. 10, in which the optical measurement system 80 comprises three measurement zones 21, 22 and 23, and a single lighting 81 and detection / analysis system 84 connected to the measurement zones by optical fibers 85, 87 and 88.
    According to another embodiment, the in situ measurement is carried out in an identical manner to that of the embodiment shown in FIG. 10, except that the optical measurement system comprises three reflectors 45, 45 'and 45 ”such as described in relation to FIG. 2, respectively arranged at the ends of the measurement zones 21, 22 and 23.
    According to one embodiment, illustrated in FIG. 12, the optical measurement system 90 comprises means 95 for protecting the light source 91 and / or the spectrometer 94. Such protection means are useful for example during operation when the optical measurement system is cold, in order to prevent fouling of the optical elements, as already explained above. These protection means may include a flap that can be controlled by measuring the temperature of the exhaust gases, an air barrier between the light source 91 or the spectrometer 94 and the exhaust gases passing through the measurement zone 21, a specific coating, for example for thermal insulation or to prevent the adhesion of liquid or solid particles, of the surface or surfaces separating the light source 91 from the exhaust gases or the spectrometer 94 from the exhaust gases, or a means for heating said surfaces. It can also be a specific geometry of the optical sensor, not shown in Figure 12.
    According to one embodiment, illustrated in FIG. 13, the optical measurement system 90 is of the type represented in FIG. 2, and the optical path is from UV radiation is substantially tangent to the path P of the exhaust gases, the system optic being for example positioned at a bend in the exhaust line 20.
    According to another embodiment, illustrated in FIG. 14, the optical measurement system 90 is of the type shown in FIG. 2, and the optical path is from UV radiation is substantially parallel to the path P of the exhaust gases. The light source 91 and spectrometer 94 assembly are located at the outlet of the exhaust line.
    The present invention advantageously applies to the monitoring of polluting emissions of exhaust gases from an internal combustion engine in the field of transport, in particular that of rolling vehicles, but also to the monitoring of polluting emissions in the fixed applications such as industrial smoke from combustion plants.
    In the field of transport, in particular that of rolling vehicles, the present invention can be used to monitor post-combustion depollution systems, and possibly control, that is to say intervene in the adjustment, of such depollution systems. .
    The present invention can also be applied to the field of monitoring polluting emissions of exhaust gases from an internal combustion engine of ships, in particular monitoring of NOx in areas with controlled emission (ECA), in addition to monitoring SOx in controlled sulfur emission zones (SECA).
    权利要求:
    Claims (17)
    [1" id="c-fr-0001]
    1. Method for in situ measurement of the concentration ([X]) of at least one gaseous chemical species contained in exhaust gases (10) circulating in an exhaust line (20) and of the temperature (T) said exhaust gas by means of an optical measurement system (40, 40 ', 40 ”, 70, 80, 90), said optical measurement system comprising at least one light source (41, 4Γ, 41”, 71 , 81, 91) and a spectrometer (44, 44 ', 44 ”, 74, 84, 94), comprising the following steps:
    - the emission by the light source of UV radiation (42) through said exhaust gases within a measurement zone (21, 22, 23) located in the exhaust line (20);
    - the detection by the spectrometer of at least part of said UV radiation having passed through said exhaust gases (43) in said measurement zone (21, 22, 23) and the generation of a digital signal of the light intensity (50) as a function of the wavelength (W) of said part of the UV radiation having passed through said exhaust gases;
    - the estimate of the concentration ([X]) of said chemical species and of the temperature (T) of said exhaust gases from said digital signal (50).
    [2" id="c-fr-0002]
    2. The method of claim 1, wherein the optical measurement system further comprises a reflector (45, 45 ', 45 ”), and said method comprises a step in which said UV radiation (42) emitted by the light source (41) passes through said exhaust gases in the measurement zone (21) and is then reflected by the reflector (45, 45 ', 45 ”), passes through said exhaust gases again in the measurement zone (21) in the opposite direction to then be detected by the spectrometer (44).
    [3" id="c-fr-0003]
    3. Method according to one of claims 1 or 2, comprising a prior step of calibrating the optical measurement system to provide a digital reference signal of the light intensity as a function of the wavelength, preferably by emission of said UV radiation through a reference gas, for example a reference gas containing none of the chemical species to be measured, and by detecting at least a portion of said UV radiation having passed through said reference gas to provide a digital reference signal of the light intensity as a function of the wavelength of said part of the UV radiation having passed through said reference gas.
    [4" id="c-fr-0004]
    4. Method according to one of the preceding claims, in which the step of estimating the concentration ([X]) of said chemical species and of the temperature (T) of said exhaust gases (10) comprises:
    - determining the absorbance (A) of said exhaust gases as a function of the wavelength from said digital light intensity signal (50) as a function of the wavelength of said part of the UV radiation having passed through said exhaust gas (43) and a digital reference signal;
    - determining the concentration ([X]) of said at least one chemical species from the absorbance of said exhaust gases and predetermined absorbance, temperature and pressure characteristics of said chemical species;
    the determination of the temperature (T) of said exhaust gases by modification of the molar extinction coefficient of the absorbance of said chemical species extracted from the absorbance of said exhaust gases, said modification being a shift in the length d wave or a change in amplitude or a combination of both.
    [5" id="c-fr-0005]
    5. The method of claim 4, wherein the absorbance (A) of said exhaust gas (10) is a function of the absorbance length, the number of density of molecules of said chemical species and the extinction coefficient molar.
    [6" id="c-fr-0006]
    6. Method according to one of the preceding claims, in which the UV radiation (42) emitted has a wavelength between 180 and 400 nm, preferably between 180 and 280 nm, and even more preferably between 180 and 240 nm.
    [7" id="c-fr-0007]
    7. Method according to one of the preceding claims, in which the concentration of at least one, and preferably several, gaseous chemical species contained in the exhaust gases, and included in the list constituted by: NO, NO, is measured. 2 , N 2 O, BTX, SO 2 , H 2 S, O 3 , O 2 , H 2 O, aldehydes such as acetaldehyde or formaldehyde, non-aromatic hydrocarbons such as acetylene or buta-1,3diene .
    [8" id="c-fr-0008]
    8. Method according to one of the preceding claims, in which the concentration of at least two gaseous chemical species is measured simultaneously, and preferably at least the concentration of NO and the concentration of NO 2 .
    [9" id="c-fr-0009]
    9. The method of claim 7, applied to the control of NOx at the outlet of a pollution control system (60, 61), preferably at the outlet of a selective catalytic reduction system (SCR), or applied to the control of NOx in upstream and downstream of a pollution control system (60, 61), in which at least the concentration of NO and the concentration of NO 2 are measured, preferably to estimate the real-time conversion of NOx to N 2 by said system depollution.
    [10" id="c-fr-0010]
    10. Method according to one of the preceding claims, in which the concentration of at least one gaseous chemical species chosen from sulfur-containing chemical species SO 2 and H 2 S is measured, and preferably both.
    [11" id="c-fr-0011]
    11. Method according to one of the preceding claims, in which the concentration of at least NH 3 is measured.
    [12" id="c-fr-0012]
    12. The method of claim 11, applied to the control of NH 3 upstream or downstream of a selective catalytic reduction system (SCR), in which the evolution of the NH 3 concentration is monitored upstream or downstream of the selective catalytic reduction system (SCR).
    [13" id="c-fr-0013]
    13. Method according to one of the preceding claims, in which the exhaust gases come from an internal combustion engine.
    [14" id="c-fr-0014]
    14. Method according to one of the preceding claims, wherein said UV radiation passes through said exhaust gases along an optical path substantially perpendicular to the path (P) of said exhaust gases.
    [15" id="c-fr-0015]
    15. Method according to one of the preceding claims, in which the in situ measurement is carried out downstream of at least one exhaust gas pollution control system (60, 61) such as a diesel oxidation catalyst (DOC) , a selective catalytic reduction system (SCR) or a particulate filter (FAP).
    [16" id="c-fr-0016]
    16. Method according to one of the preceding claims, in which the in situ measurement is carried out upstream of at least one exhaust gas depollution system (60, 61) such as a diesel oxidation catalyst (DOC) , a selective catalytic reduction system (SCR) or a particulate filter (FAP).
    [17" id="c-fr-0017]
    17. Optical measurement system (40, 40 ', 40 ”, 70, 80, 90) for in situ measurement of the concentration ([X]) of at least one gaseous chemical species contained in exhaust gases ( 10) circulating in an exhaust line (20) and of the temperature (T) of said exhaust gases according to one of the preceding claims, said system comprising:
    - a light source (41, 41 ', 41 ”, 71, 81, 91) capable of emitting UV radiation (42) through said exhaust gases within a measurement area (21, 22, 23 ) located in the exhaust line, said light source being preferably positioned so as to emit said UV radiation along an optical path substantially perpendicular to the path (P) of said exhaust gases;
    - a spectrometer (44, 44 ', 44 ”, 74, 84, 94) capable of detecting at least part of said UV radiation having passed through said exhaust gases (43) in said measurement zone (21, 22, 23) and generating a digital signal of light intensity (50) as a function of the wavelength (W) of said part of the UV radiation having passed through said exhaust gases (43);
    - means for analyzing and processing said signal to determine the concentration ([X]) of said chemical species and the temperature (T) of said exhaust gases from said digital signal (50).
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    同族专利:
    公开号 | 公开日
    EP3658895A1|2020-06-03|
    JP2020528151A|2020-09-17|
    FR3069641B1|2019-07-19|
    EP3658895B1|2021-06-09|
    WO2019020326A1|2019-01-31|
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    法律状态:
    2019-02-01| PLSC| Search report ready|Effective date: 20190201 |
    2019-07-25| PLFP| Fee payment|Year of fee payment: 3 |
    2020-07-28| PLFP| Fee payment|Year of fee payment: 4 |
    2021-07-26| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1757140A|FR3069641B1|2017-07-27|2017-07-27|METHOD AND SYSTEM FOR OPTICALLY MEASURING THE CONCENTRATION OF EXHAUST GAS CASES|
    FR1757140|2017-07-27|FR1757140A| FR3069641B1|2017-07-27|2017-07-27|METHOD AND SYSTEM FOR OPTICALLY MEASURING THE CONCENTRATION OF EXHAUST GAS CASES|
    JP2020504175A| JP2020528151A|2017-07-27|2018-07-03|Methods and systems for optically measuring the concentration of gas species in exhaust gas|
    EP18737870.8A| EP3658895B1|2017-07-27|2018-07-03|Method and system for optical measurement of the concentration of chemical species in an exhaust gas|
    PCT/EP2018/067930| WO2019020326A1|2017-07-27|2018-07-03|Method and system for optically measuring the concentration of gaseous species of exhaust gases|
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