The invention relates to a method for operating an optical measuring system for measuring the concentration of a target gas component (ZG) in a measured gas, comprising a wavelength-tunable temperature-stabilized laser light source, wherein an instantaneous base current IDC_ZG,act corresponding to a wavelength λZG of a target gas absorption line is set so that a wavelength distance ΔλDC defined during the calibration between a target gas absorption line for a target gas component (ZG) and a reference gas absorption line for a reference gas component (RG) is maintained. The invention furthermore relates to a system for carrying out the method.
Optical measuring systems for measuring the concentration of a gas component in a measured gas, based on laser absorption spectroscopy (LAS), are known from the prior art in a wide variety of embodiments, as are a multitude of different methods for operating such an optical measuring system, such as wavelength modulation spectroscopy (WMS) and direct absorption spectroscopy (DAS). In LAS, exact setting of the laser wavelength to the wavelength of the absorption line for the target gas plays an important role in general. During calibration, the laser wavelength is usually defined by way of the operating point of the Peltier temperature (base laser temperature) and the base current IDC of the laser light source. However, long-term changes in the laser and the influence of the outside temperature result in a different wavelength for the selected operating point, which deviates from the absorption wavelength of the target gas, even if the base current IDC remains unchanged. Base current usually denotes a direct current (DC) having a maximum at the absorption line, with larger and smaller current values traversed around this, when the absorption line is being scanned. As a consequence, these changes also cause the sensor calibration to deviate from the specification limits, which then often necessitates a re-calibration of the optical measuring system.
So as to ensure that the wavelength of the target gas remains accurate (in particular in the absence of the target gas), usually one or more absorption lines for a reference gas are used, and the line locking principle is applied. The reference gas is either essentially permanently present in the process gas or is accommodated somewhere in the sensor itself, enclosed in a cuvette, for example. The cuvette can be implemented, for example, in the optical measuring path or in a special optical reference path (this requires a beam splitter and a further photodiode).
Often, it is not possible or useful to use the target gas itself as the reference gas, for example when this is not stable over a long time, when the line width associated therewith is too thin, which results from too short an absorption path and leads to a low absorption signal, or when this is too dangerous to produce or during operation.
As an alternative, a different gas (reference gas), which has one or more absorption lines in the vicinity of a target wavelength, can be used instead of the target gas. Reference is made to EP 2 307 876 B1 by way of example. This patent uses two CH4 gas absorption lines to exactly reference the CO gas absorption line in the center. Often, however, the tuning range of the laser light source is not sufficiently wide to accurately reference a target gas absorption line in this way.
EP 2 307 876 B1 discloses a method for detecting at least one target gas by way of laser spectroscopy, using a laser light source having an emission wavelength that is monochromatic and tunable by varying the operating temperature or the operating current. So as to calibrate the wavelength scale of the laser light source relative to the varied operating temperature or the varied operating current, in the wavelength range of a band of the at least one target gas, a first laser light source tuning step is carried out across a first tuning width, wherein at least two absorption lines for a reference gas and at least one absorption line for the at least one target gas are present. Thereafter, a second laser light source tuning step is carried out across a second tuning width in the wavelength range of the band of the at least one target gas, wherein the second tuning width is narrower than the first tuning width, and wherein at least one of the at least one absorption line for the at least one target gas is present. The target gas and the reference gas are different gases. The first tuning step for calibrating the laser current or the laser temperature is carried out once with the absolute wavelength scale, and the second tuning step for detecting the at least one target gas is carried out consecutively several times. The second tuning width is compared to a calculated absorption spectrum, wherein non-iterative curve fitting using a linear regression algorithm is employed so as to calculate the concentration of the at least one target gas in one step. This procedure requires a reference gas that has at least two absorption lines in the vicinity of the target gas absorption line, which are within the tuning range of the laser. Moreover, this procedure is time-consuming since it requires that two reference lines be detected and evaluated.
For activating a wavelength-tunable laser diode in a spectrometer using no reference gas, it is known from DE 10 2013 202 289 A1 to predefine a power-time function, in accordance with which the laser diode is tuned periodically over a wavelength range, by ascertaining a current profile, which is used to activate the laser diode, from the power-time function and the measured values of the voltage present at the laser diode. The current profile that is used to directly activate the laser diode is generated by a control unit as a function of the control deviation between the power consumption (actual variable) of the laser diode and the predefined power-time function (target variable), wherein the voltage present at the laser diode and the current through the laser diode are continuously detected, for example measured, and the power consumption of the laser diode is ascertained continuously by multiplying the measured current and voltage values. No reference gas is used therein, and thus a different wavelength range is detected when the temperature of the Peltier element (Peltier temperature) on which a laser chip is disposed and/or the outside temperature change, even though the power-time function is predefined. This method is too imprecise for referencing a target gas. Moreover, the entire voltage across the laser is measured, which is too imprecise for determining the wavelength.
If only one reference gas line, which is not the target gas line, is available for the use of a reference gas, it is essential to ensure that the wavelength distance ΔλDC between the target gas and the reference gas is kept constant during operation for different laser currents, and thus different laser temperatures. Moreover, the distance must also remain constant when the laser ages. In principle, it would be possible to simply scan a certain wave range. However, the detection limit is drastically limited due to present noise, resulting from optical interference phenomena, for example, and the presence of absorption lines for other gases in the measured spectrum. It is therefore important to adhere to the wavelength distance very precisely.
The wavelength distance between the target gas and the reference gas is typically set by a constant current distance ΔI. Due to the non-linear DC tuning behavior of the laser, a shift (drift) of the operating point, for example as a result of the influence of the outside temperature on the temperature stabilization or aging of the laser/electronics, results in a distance error for the wavelength distance. This results in the target gas component (absorption line for the target gas) being presumed to be in an incorrect location. In some instances, this results in considerable measurement errors.
Proceeding from this, it is the object of the claimed invention to propose a different, more precise, effective and easy to implement option for keeping the wavelength distance between the target and reference gas lines constant, despite changing laser properties, such as operating current, operating temperature or long-term drift.
This object is achieved according to the invention by a method for operating an optical measuring system for measuring the concentration of a target gas component in a measured gas having the features of described herein and by a system in the form of a measuring system described herein. Further advantageous embodiments can be derived from the respective dependent claims.
The core idea of the invention is, instead of using a fixed current difference value, to set the current difference in such a way that a previously defined relative temperature difference is maintained between the reference and target gas (peak) positions, which is to say between the respective absorption lines, for the calculation of the presumed wavelength position of the target gas. This temperature difference is calculated from the difference of the temperatures that are generated by the respective introduced electrical powers at an internal resistance of the laser light source at the peak positions of the target and reference gases at the time of calibration. This relative temperature difference is proportional to the wavelength distance of the absorption lines for the target and reference gases, and thus this procedure ensures that the target wavelength can always be exactly determined.
For example, this method advantageously allows applications in which reference gas and target gas absorption lines are significantly distanced from each other to be easily implemented. Monitoring for methane leaks shall be mentioned here by way of example, where, in addition to CH4, C2H6 (ethane) also has to be measured to confirm that natural gas is involved. The reference gas used is methane (which, in this case, also represents the second target gas), which is accommodated in the optical path of the laser in the sensor for this purpose. Depending on the selected absorption lines, the distance between the reference gas (methane) and the target gas (ethane) is between 0.6 and 1.0 nm here. Since this distance is considerable, it is no longer possible to use a fixed current value. Additionally, there is an advantage in that the calibration is particularly simple, as compared to the conventional calibration methods known from the prior art.
The abbreviations RG and ZG used hereafter denote a reference gas, or a reference gas component in a gas, and a target gas, or a target gas component in a measured gas. The designations DC and AC used are common and thus known to a person skilled in the art as designations for DC voltage/direct current and AC voltage/alternating current. These refer to electrical currents, voltages and/or powers and indicate the respective type. Moreover, the abbreviation L is used for the laser light source or, in general, for the laser. The abbreviations RG, ZG, DC, AC and L are used for clarification in the claims and in the overall description, and in particular in the formulas below. The base current IDC denotes, in summary, all the base currents corresponding to the respective operating states (calibration, instantaneous base current) and associated gases (RG, ZG).
According to the invention, in the method, during operation, a relative temperature difference in the laser light source, defined in advance during the calibration, between the operating points, selected at the time of calibration, of the reference gas (RG), with a base current IDC_RG,cal, and the target gas component (ZG), with a base current IDC_ZG,cal, is maintained by determining the required instantaneous base current IDC_ZG,act for the target gas component, as a function of an instantaneous base current IDC_RG,act for the reference gas.
The calibration of the measuring system is preferably carried out with the reference gas and the target gas. During the calibration, the base currents IDC_RG,cal and IDC_ZG,cal, assigned to the gas absorption lines for the reference gas RG and of the target gas component ZG are established, the associated electrical powers PDC_RG,cal and PDC_ZG,cal of the laser light source are determined, and a power difference ΔPDC, cal is found therefrom, which is stored.
According to the invention, moreover, during operation of the measuring system, the electrical power PDC_RG,act of the laser source assigned to the gas absorption line for the reference gas is then ascertained, the electrical power PDC_ZG,act of the laser source assigned to the gas absorption line for the target gas ZG is determined as the sum of the electrical power PDC_RG,act and the power difference ΔPDC, cal, and the assigned base current IDC_ZG,act is calculated from the electrical power PDC_ZG,act of the laser source thus determined.
In other words, this means that, during the calibration, the DC laser currents of the peak positions of the reference gas and the target gas are established, the electrical DC power dropping across the internal resistance of the laser is ascertained for the two peak positions by detecting the internal resistance of the laser at the respective current position or, alternatively, an equivalent variable, for example using lock-in technology. At the time of calibration, the power difference ΔPDC, cal of the DC powers, or at least an equivalent variable, is ascertained and stored in the sensor. The power difference is preferably determined according to formula F 10 listed below. As an alternative, it would also be possible to store the variables indicated in formula F 10 in the sensor.
During operation of the measuring system, the electrical DC power dropping across the internal resistance of the laser is determined for the instantaneous peak position of the reference gas. The internal resistance measurement can be implemented, in particular, by lock-in technology. Since the operating point may shift due to drift, the electrical power PDC_RG,act is recalculated on a regular basis (and thus cannot be assumed to be a fixed value). Moreover, the instantaneous electrical power at the peak position for the target gas is determined by adding the instantaneous power for the reference gas peak and the power difference. From the instantaneous power of the peak for the target gas, the DC current for the peak position thereof is preferably ascertained according to formula F 11 listed below. Thereafter, the measuring scan for the target gas is carried out at the ascertained peak position for the target gas, and the gas concentration is ascertained therefrom. The base current defines the position at which the absorption characteristic curve has a maximum. Scanning with larger and smaller current values is carried out around this maximum to ascertain the concentration.
The proposed method is used for the initial calibration of the measuring system by the manufacturer and can also be utilized by the user for potentially necessary subsequent calibration.
In wavelength modulation spectroscopy, as is customary, a wavelength-tunable temperature-stabilized laser light source is used, which periodically varies a central base wavelength of the laser light of the laser light source by changing the base current via a relevant absorption line for the gas component at an operating point and, at the same time, modulates the same with a frequency (f) and a determinable amplitude by way of a modulation device. Using a light detector, the intensity of the laser light after it has passed through the measured gas is detected. An evaluation unit is used, which comprises means for the phase-sensitive demodulation of a measuring signal generated by the light detector at the frequency (f) and/or one of the harmonics thereof, wherein the laser light source is operated in a current-modulated manner with a base current IDC and a modulation current IAC and emits a laser beam of the wavelength having a wavelength modulation amplitude ΔλAC, and the wavelength modulation amplitude ΔλAC of the laser light is kept constant by way of variable setting of the current modulation amplitude ΔIAC.
However, long-term changes in the laser may make it necessary to adapt the base laser temperature. However, this also necessitates a correction of the previously calculated power difference ΔPDC,cal. If the laser temperature is being varied, formula F 15 should be preferred over formula F 11 for calculating the base current IDC_ZG,act. For this purpose, the laser temperature is stored at the time of calibration.
According to a preferred method step, the respective internal resistances are required for calculating the electrical power at the respective base currents (for the target and reference gases). It should be noted that the exact internal resistance may iterate only after multiple measurements.
The internal resistance RI of the laser light source is preferably determined from a voltage/current characteristic curve for the laser light source in which the voltage drop UL across the laser light source is recorded as a function of the base current IDC. The respective internal resistances are ascertained at the peak positions of the reference gas and the target gas. The voltage/current characteristic curve of the laser light source is usually recorded for the first time during the calibration of the optical measuring system. It is not necessary to measure the entire curve, but only a region around the operating point, so as to correctly determine the respective internal resistance RI from the slope in this region. A multitude of measurements can be carried out in the region, and the result can be averaged. As an alternative, the slope can also be ascertained using lock-in technology, which has the advantage that noise is reduced. The resistance values are also ascertained during operation on a regular basis, and preferably these are re-determined during every concentration measurement.
During calibration and during regular operation of the optical measuring system, an evaluation unit comprising lock-in technology is preferably used for determining the concentration of a target gas component, so as to achieve noise reduction in the known manner, in particular in order to considerably lower the noise caused by the 1/f signal. A lock-in amplifier, which is also sometimes referred to as a phase-sensitive rectifier or carrier frequency amplifier, is an amplifier for measuring a weak electrical alternating signal, which is modulated with a reference signal having a known frequency and phase. The device represents an extremely narrow-band bandpass filter, thereby improving the signal-to-noise noise ratio. The advantage when using such a device is that DC voltages and AC voltages having different frequencies and noise are efficiently filtered.
According to the invention, the method described above is based on the formulas provided below. These are used during calibration and/or during operation. Values from calibration are denoted by “cal” and values from operation are denoted by “act.”
Heretofore, the instantaneous current position of the target gas (ZG) is determined in relative terms by the position of the reference gas (RG) using the following formula:
IDC_ZG,act=IDC_RG,act+ΔI (F 1)
where ΔI is a fixed current value, which is established during calibration:
ΔI=IDC_ZG,cal−IDC_RG,cal (F 2)
Due to the aforementioned non-linear DC tuning behavior of the laser, this procedure is not sufficiently exact for determining the position of the ZG. It is apparent from
that a wavelength change can be described by a temperature change, where neff is the effective refractive index, and Leff is the effective resonator length of the laser. Taking into consideration that the first term on the right side of the above formula is dominant over the second term, a wavelength change is given by:
So as to calculate the presumed position of the target gas, instead of using a fixed current difference value (that was determined during calibration according to formula F 2), the current difference is set during ongoing operation in such a way that a defined temperature difference ΔTact is maintained between the reference and target gas (peak) positions. This results in the following temperature at the instantaneous position of the target gas:
TZG,act=TRG,act+ΔTact (F 5)
wherein the temperature at the position of the reference gas peak is given by:
TRG,act=PDC_RG,act·Rth,act=IDC_RG,act2·RI RG,act·Rth,act (F 6)
wherein the electrical power is converted via the thermal resistance Rth,act into the temperature TRG,act, and the power is produced by the laser current IDC_RG,act in the internal resistance RI RG,act.
The instantaneous temperature TZG,act at the position of the target gas peak is coupled to the sought laser current IDC_ZG,act via the thermal resistance and electrical resistance:
TZG,act=PDC_ZG,act·Rth,act=IDC_ZG,act2·RI ZG,act·Rth,act (F 7)
If the laser temperature does not change during operation, then:
The aforementioned temperature difference ΔTcal is calculated as the difference of the temperatures that are generated by the respective introduced electrical powers at the internal resistance at the peak positions of the target and reference gases at the time of calibration. Since the temperature difference is proportional to the wavelength difference between ZG and RG, this procedure ensures that the target wavelength is always exactly determined.
By inserting formulas (F 6), (F 7) and (F 8) in formula (F 5), the sought laser current at the position of the target gas is found:
wherein a power difference (“fixed power”) results using the values at the time of calibration:
ΔPDC,cal=IDC_ZG,cal2·RI ZG,cal−IDC_RG,cal2·RI RG,cal (F 10)
Assuming that the thermal resistance does not change during operation (Rth,act=Rth,cal), the following results for the peak position of the target gas:
It should be noted that the exact internal resistance RI ZG,act is not known initially and would have to be measured (at the location IDC_ZG,act). After running through the formula several times, or after multiple measurements, however, the value iterates very quickly, and the internal resistance is correctly ascertained at the location IDC_ZG,act.
If, additionally, the operating point of the base laser temperature TL changes (for example, if the Peltier temperature is adapted during operation so as to compensate for excessively large wavelength shifts on the current scale due to the adaptation of the base laser temperature), from the constant relative temperature change condition:
then the following relationship for the instantaneous temperature difference follows:
wherein the temperatures are to be used in Kelvin. The resulting current is given by:
If a change in the thermal resistance can be neglected, it again follows that:
It is commonly known that each laser light source circuit diagram can be replaced with an equivalent circuit, which comprises a laser emitter (active zone) and an internal resistance RI connected in series thereto. As soon as a base current IDC flows through the laser light source, a voltage UL is present at the laser light source, which in part drops across the laser emitter as a partial voltage UE and across the internal resistance RI as a partial voltage URI, where UE typically has a value of 0.9 to 1.1 V, depending on the laser type (having a wavelength close to that common in the telecom industry). In the case of WMS, additionally a modulation current IAC is added to the base current; however, this does not affect this method since the temperature changes average out over time.
The instantaneous DC power at the position of the reference gas peak is calculated from the base current IDC_RG,act flowing through the laser light source, and the voltage drop URI_RG,act occurring at the internal resistance RI_RG,act as
PDC_RG=IDC_RG,act·URI_RG,act=IDC_RG,act2·RI RG,act (F 166)
The calibration of the optical measuring system takes place substantially according to the common method that is routine to the person skilled in the art by way of a known reference gas, which may also be a target gas, and the actual target gas itself. So as to establish the operating point of the laser light source, first the temperature of the temperature-stabilized laser light source is varied until the absorption signals for the reference and target gases are detected at a desired operating point. Thereafter, the power difference is ascertained and stored.
The system according to the invention is composed of a measuring system for carrying out the method, comprising a modulation device (4) for providing the base current IDC for the laser light source, a receptacle for the measured gas, a light detector, and an evaluation unit (6) connected to the light detector and the modulation device, means for detecting the voltage present at the laser light source, means for detecting the laser base temperature, means for ascertaining the internal resistance of the laser light source, and means for controlling the base currents IDC for the reference gas (RG) and the target gas (ZG). It is particularly preferred when the reference gas is disposed in the optical path of the laser in the sensor, so that the laser beam emitted by the laser light source first passes through the reference gas, and thereafter through the measured gas, to the light detector. This allows for extremely compact design of the entire measuring system and production of easy-to-handle and easy-to-transport gas detection devices.
The features and feature combinations mentioned above in the description, and the features and feature combinations mentioned hereafter in the description of the figures and/or shown only in the figures, can be used not only in the respective indicated combinations, but also in other combinations, or alone. It is not necessary for all the features recited in the claims to be implemented to carry out the invention. It is also possible to replace individual features of the independent or dependent claims with other disclosed features or feature combinations.
The invention will be described again in more detail hereafter based on the accompanying drawings. In the drawings, in schematic illustrations:
In a schematic illustration,
In the subsequent second method step S2, which is to say during operation of the measuring system 1, initially the electrical DC power dropping across the internal resistance of the laser is ascertained for the instantaneous peak position of the reference gas by measuring the internal resistance using lock-in technology, then the instantaneous electrical DC power at the peak position for the target gas is calculated by adding the instantaneous DC power for the reference gas peak and the DC power difference between the reference gas and the target gas ascertained during calibration. Thereafter, the DC current for the peak position thereof is ascertained, wherein according to formula F 11 or F 15 the internal resistance of the target gas from the preceding measurement is used for this purpose. If F 15 is used, additionally the ratio of the instantaneous laser temperature to the calibration laser temperature is used. The laser temperature is stored at the time of calibration.
In the subsequent third method step S3, the actual measuring scan for the target gas is carried out based on the ascertained peak position for the target gas, and the gas concentration is ascertained therefrom.
The method steps S2 and S3 are preferably carried out multiple times in a loop, wherein the base current IDC_ZG for the target gas position can be adapted between the runs, if the instantaneous base current IDC_ZG, act deviates from the ideal base current IDC_ZG, cal, which was ascertained during the calibration of the optical measuring system.
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