CN102007397A - Gas analyzing apparatus with built-in calibration gas cell - Google Patents
Gas analyzing apparatus with built-in calibration gas cell Download PDFInfo
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- CN102007397A CN102007397A CN2008801286598A CN200880128659A CN102007397A CN 102007397 A CN102007397 A CN 102007397A CN 2008801286598 A CN2008801286598 A CN 2008801286598A CN 200880128659 A CN200880128659 A CN 200880128659A CN 102007397 A CN102007397 A CN 102007397A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/27—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using photo-electric detection ; circuits for computing concentration
- G01N21/274—Calibration, base line adjustment, drift correction
- G01N21/276—Calibration, base line adjustment, drift correction with alternation of sample and standard in optical path
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/39—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using tunable lasers
- G01N2021/396—Type of laser source
- G01N2021/399—Diode laser
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/12—Circuits of general importance; Signal processing
- G01N2201/128—Alternating sample and standard or reference part in one path
- G01N2201/1285—Standard cuvette
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Abstract
A gas analyzing apparatus for laser absorption spectroscopy measurement includes a laser light source to generate laser beam with a specific wavelength absorbed by a component being measured in sample gas, a laser light source drive controller to control driving of the laser light source, an optical detector arranged at a location where the laser beam is received, a gas cell for measurement of the sample gas which is arranged on an optical path of the laser beam going from the laser light source to the optical detector, and a computing unit to calculate a concentration of the component being measured in the sample gas in accordance with a detection signal of the optical detector. Further, the gas analyzing apparatus has at least one calibration gas cell where calibration gas is filled with, and a calibration gas cell mounting mechanism capable of locating one of the calibration gas cells in a removable manner on the optical path of the laser beam.
Description
Technical field
The present invention relates to a kind of gas analyzing apparatus that uses the laser absorption spectrum technology.
Background technology
Using laser absorption spectrum to carry out under the situation of gasmetry, can obtain concentration in theory according to lambert-Bill (Lambert Beer) law basically.But it is limited that optics is adjusted, thereby be difficult to theory in full accord.With regard to reality, general zero gas, the known gas of concentration of using is made inspection amount line, and absorbance is scaled concentration.
At this moment, calibration gas is imported measurement with air chamber (Gas Cell), carry out sensitivity correction according to its output.In other method, all the time be provided with other optical system, proofread and correct with air chamber and photodetector, utilize semi-transparent semi-reflecting lens to separate to take out and import to proofread and correct and use air chamber, possess the function (with reference to patent documentation 1) of supervision corrected value thus as the part of the laser of measuring light.
Patent documentation 1: TOHKEMY 2005-106546 communique
Summary of the invention
The problem that invention will solve
Use to measure under the situation of proofreading and correct, importing to measure at the gas that carries out timing and all need to proofread and correct usefulness at every turn and use air chamber with air chamber.The flow passage structure that for this reason, need have special gas pipe arrangement and transfer valve etc.Also must keep proofreading and correct the gas of usefulness.This apparatus structure complexity, and larger.In addition, calibration gas also adsorb sometimes or stay in the pipe arrangement that is used for measuring with air chamber, valve or measure with air chamber itself, therefore on measuring accuracy, also have problems.
All the time possess the analytical equipment of proofreading and correct with air chamber and have the advantage that can monitor corrected value all the time.But, can be used in the light quantity measured with the laser of air chamber owing to semi-transparent semi-reflecting lens dies down, therefore measure the signal to noise ratio (S/N ratio) used in the photodetector (S/N: the reduction ratio of signal and noise).And monitor and use photodetector with also possessing the photodetector except possessing measurement that permeametry is detected with the light of air chamber, therefore needing increases the adjustment that characteristics such as the sensitivity between two photodetectors and the linearity are carried out, and has also caused the complicated of device.
The objective of the invention is to, be used for the analytical equipment that laser absorption spectrum is measured, do not need to import calibration gas with air chamber, and also do not need additionally to be provided with photodetector to measuring.
The scheme that is used to deal with problems
In the present invention, in order to address these problems, can only will to proofread and correct when needed and be inserted on the light path with air chamber.
That is, analytical equipment of the present invention possesses: LASER Light Source, and it produces the laser as measuring light, and this measuring light has the specific wavelength that is absorbed by the measuring object composition in the sample gas; The LASER Light Source driving control device, its driving to LASER Light Source is controlled; Photodetector, it is disposed at the position that receives laser; Sample air is measured and is used air chamber, and it is disposed on the light path of the laser from the LASER Light Source to the photodetector; Air chamber is used at least one correction, and its inclosure has calibration gas; Proofread and correct and use the air chamber installing mechanism, it can releasably be disposed on the laser optical path with a correction in the air chamber with air chamber with proofreading and correct; And arithmetic unit, its detection signal according to photodetector is calculated the concentration of the measuring object composition in the sample air.
In the following description, when specifically representing wavelength, use wave number to replace wavelength.Wave number is corresponding with wavelength, and therefore in the present invention, " wavelength " is used as comprising the notion of " wave number ".
Use air chamber by having in addition to proofread and correct, do not need that gas is imported measurement and use air chamber, also do not need to have the gas-holder of proofreading and correct usefulness, so correct operation is simple and apparatus structure is also uncomplicated.
In addition, releasably be inserted on the light path that is used in gasmetry, therefore do not need optical system is appended new parts owing to will proofread and correct with air chamber.Also owing to do not utilize semi-transparent semi-reflecting lens to separate with laser, therefore can keep the light quantity of laser in addition to measuring.And, proofread and correct with photodetector owing to use to measure, therefore can realize the correction that degree of accuracy is high.
Can make the correction air chamber of plurality of specifications by change gaseous species, concentration, pressure and other parameters, thereby become the mode that can realize that higher degree is proofreaied and correct.
As LASER Light Source, can use the laser diode of the light that only produces single wavelength, but, can use the LASER Light Source that can change wavelength in order to expand measuring object, analytic target to be had versatility or improves signal to noise ratio (S/N ratio).As LASER Light Source, generally use the narrower DFB laser of oscillation light spectral line width (Distributed FeedBackLaser: diode distribution feedback laser), but then do not limit its kind so long as can reach the LASER Light Source of same technical requirement.Under the situation of using the LASER Light Source can change wavelength, the LASER Light Source drive control device controls is to the driving of LASER Light Source, makes the laser that produces specific wavelength when the measuring object composition is measured.
In the Wavelength variable LASER Light Source, can be by drive current, this class parameter of laser bodies temperature be controlled and are regulated the Wavelength of Laser that is produced.Therefore, be preferably the LASER Light Source driving control device and possess wavelength variation data maintaining part, this wavelength variation data maintaining part keeps the wavelength variation data, Wavelength of Laser that this wavelength variation data representation is produced and the relation between the parameter, when the measuring object composition is measured, the LASER Light Source driving control device is according to the driving of the wavelength variation Data Control that is kept to LASER Light Source, so that LASER Light Source produces the laser of specific wavelength.
As an example of Wavelength variable LASER Light Source, can use following LASER Light Source: possess the thermoregulation mechanism that the temperature of laser bodies is regulated, can the optical maser wavelength of generation be changed by the temperature of regulating laser bodies.In this case, be preferably the LASER Light Source driving control device and carry out following control: provide fixing reference current to the laser bodies that is used for the driving laser light source, provide temperature control electric current to the thermoregulation mechanism that is used to regulate the laser bodies temperature.In the time will making the optical maser wavelength that produces from wavelength variable LASER Light Source fixedly, control the electric current that provides to thermoregulation mechanism so that the temperature of laser bodies is fixed; When the optical maser wavelength that will make generation changes, the electric current that control provides to thermoregulation mechanism so that the temperature of laser bodies change.
Under the situation of the laser that uses Wavelength variable LASER Light Source generation specific wavelength, need the drive condition of setting laser light source exactly, therefore be preferably and proofread and correct wavelength variation data as required or at any time as the drive condition setting basis.Though use optical splitter can accurately adjust output wavelength,, can not use optical splitter in the present invention and setting laser wavelength exactly.Therefore, use as the peak wavelength of benchmark and based on the relation between parameter such as laser bodies temperature and the optical maser wavelength that produced the wavelength variation data are proofreaied and correct.
At this, as the preferred mode of the present invention, correction comprises the wavelength calibration air chamber with air chamber, and this wavelength calibration has the long gas of known absorption spike with enclosing in the air chamber to have.Be preferably the LASER Light Source driving control device in this case and possess wavelength variation adjustment of data portion, the absorption peak wavelength of this wavelength variation adjustment of data portion when wavelength calibration is installed on light path with air chamber comes the wavelength variation data are proofreaied and correct.
In wavelength calibration,, can more critically proofread and correct by using a plurality of absorption peak wavelength.
Also can use the device that produces this a plurality of absorption peaks by a wavelength calibration with air chamber.Specific strength is big and precipitous mutually with other absorption peak to be preferably the absorption peak that is used in wavelength calibration.If, then also can use them by comprising a plurality of this suitable absorption peaks in the absorption peak of a wavelength calibration with the air chamber generation.
But, be under one the situation, to be preferably to use and to enclose a plurality of wavelength calibration air chambers that different gas is arranged at the suitable absorption peak that produces with air chamber by a wavelength calibration.Be preferably in this case, for example this wavelength calibration comprises first wavelength calibration air chamber and the second wavelength calibration air chamber with air chamber, this first wavelength calibration is positioned at than the longer long wavelength side of specific wavelength that is used for the measuring object composition is measured with the absorption peak wavelength of the gas of enclosing in the air chamber, and this second wavelength calibration is positioned at than the long shorter short wavelength side of certain wave with the absorption peak wavelength of the gas of enclosing in the air chamber.
Other advantage of carrying out wavelength calibration is to drive laser aid and makes it produce the laser that interference effect is restricted to minimal the most suitable wavelength.
Another correction is the sensitivity correction of proofreading and correct inspection amount line data.For this reason, correction comprises at least two sensitivity correction air chambers with air chamber, and above-mentioned at least two corrections have the measuring object composition that concentration is different and concentration is known with enclosing in the air chamber.In this case, arithmetic unit possesses: inspection amount line data maintaining part, and it is kept for calculating the inspection amount line data of measuring object constituent concentration; And inspection amount line adjustment of data portion, it utilizes the absorbance that obtains when sensitivity correction is installed on the light path of laser with air chamber that the inspection amount line data of inspection amount line data maintaining part are proofreaied and correct.
Using sensitivity correction is the signal to noise ratio (S/N ratio) that can improve when the low concentration sample measured with other advantage of air chamber.Under the situation that absorbance is measured, concentration reduction along with the measuring object composition in the sample air, become not obvious with the difference of background, when the instability etc. owing to device causes the wave length shift etc. of LASER Light Source, be difficult to find correct absorption peak, cause signal to noise ratio (S/N ratio) to reduce and the measuring accuracy reduction.Therefore, preferred mode is also sensitivity correction to be disposed on the light path of laser with air chamber when measuring sample air.In this case, arithmetic unit possesses the absorbance correction portion, and this absorbance correction portion deducts the absorbance that the sensitivity correction on utilization is configured in laser when measuring sample air the light path obtains with air chamber from the absorbance of utilizing photodetector to obtain.For example, in the time will being configured in the measurement of carrying out sample air on the laser optical path as sensitivity correction with air chamber with the air chamber that the concentration of 1ppm has been enclosed the measuring object composition, even the measuring object constituent concentration of sample air is near 0, photodetector also always detects the laser that penetrating concentration is the above measuring object composition of 1ppm, therefore peak is comparatively obvious with respect to background, thereby can suppress the reduction of signal to noise ratio (S/N ratio).
The effect of invention
The application of the invention, in laser absorption spectrum is analyzed, can use a plurality of gaseous absorption lines to carry out wavelength calibration as required, can reduce the influence of interfering gas and correctly set measuring wavelength, perhaps can the amount of the inspection line adjustment of data etc. multiple correction, thereby can utilize the laser absorption spectrum of pinpoint accuracy to carry out gasmetry.
Description of drawings
Fig. 1 is the block diagram of an embodiment of summary ground expression.
Fig. 2 A is near the correction vertical view of air chamber installing mechanism that is shown specifically among this embodiment.
Fig. 2 B is that expression is as the front elevation of proofreading and correct with the supporting device of air chamber installing mechanism.
Fig. 3 schematically shows to possess an example of air chamber installing mechanism is used in a plurality of corrections with the correction of air chamber summary structural drawing.
Fig. 4 schematically shows to possess the air chamber installing mechanism is used in a plurality of corrections with the correction of air chamber other routine summary structural drawing.
Fig. 5 is the block diagram that expression can be carried out the control part of wavelength calibration.
Fig. 6 is that the expression inclosure has CH
4Wavelength calibration with the chart of the absorption spectrum of air chamber.
Fig. 7 is that the expression inclosure has H
2The wavelength calibration of the O chart of the absorption spectrum of air chamber.
Fig. 8 is the chart of the wavelength variation data after expression is proofreaied and correct.
Fig. 9 is the chart of the absorption spectrum of expression CO.
Figure 10 is the block diagram that expression can be carried out the arithmetic unit of sensitivity correction.
Figure 11 is the chart of the correction of expression inspection amount line data.
Figure 12 is the chart that expression improves the measuring method of sensitivity.
Description of reference numerals
2: LASER Light Source; 3: thermoregulation mechanism; 6: control part; 4: laser drive circuit; 8: photodetector; 10: laser optical path; 12: sample air is measured and is used air chamber; 14,14a～14d: proofread and correct and use air chamber; 16: arithmetic unit; 22: proofread and correct supporting device with the air chamber installing mechanism; 23: the air chamber retainer; 15: through hole; 30: wavelength variation data maintaining part; 32: wavelength variation adjustment of data portion; 40: inspection amount line data maintaining part; 42: inspection amount line adjustment of data portion; 44: the absorbance correction portion.
Embodiment
Show to Fig. 1 summary the analytical equipment of an embodiment.In the present embodiment, generation is the DFB laser diode that can change wavelength as the LASER Light Source 2 of the laser of measuring light, and this measuring light has the specific wavelength that is become branch to absorb by the measuring object in the sample gas.Kind to the LASER Light Source that can change wavelength is not particularly limited.For the temperature of the laser bodies of regulating LASER Light Source 2, LASER Light Source 2 is built-in with the thermoregulation mechanism 3 that is made of Peltier's element (Peltier Element).
As the LASER Light Source driving control device of control to the driving of LASER Light Source 2, possess laser drive circuit 4 and control part 6, this control part 6 is made of arithmetic processing circuit or special purpose computer or general purpose personal computer.The drive current that laser drive circuit 4 provides fixing reference current Io conduct that LASER Light Source 2 is driven according to the control signal from control part 6.For the Wavelength of Laser that produces from LASER Light Source 2 is regulated, control part 6 also provides the electric current I t of temperature control usefulness to the Peltier's element of thermoregulation mechanism 3.
Control is controlled with electric current It to temperature, make the Wavelength of Laser that produces from LASER Light Source 2 become the specific wavelength that when the measuring object constituent concentration the sample air is measured, will measure absorbance, perhaps when carrying out length scanning, comprise this specific wavelength in the sweep limit.This moment, the temperature of laser bodies was adjusted to and the corresponding fixed temperature of specific wavelength.To sample air or proofread and correct when measuring, the laser from LASER Light Source 2 generations is carried out length scanning with the absorption spectrum of the gas in the air chamber.For this reason, control so that the temperature of laser bodies changes with electric current It by 6 pairs of temperature controls of control part.
From LASER Light Source 2 to photodetector 8 measurement dispose sample air with the light path 10 of laser and measure with air chamber 12.Measuring with air chamber 12 is circulation chambers, the circulation sample air.
This analytical equipment possesses encloses at least one correction air chamber 14 that calibration gas is arranged.As the kind of proofreading and correct, wavelength calibration is arranged with air chamber and sensitivity correction air chamber with air chamber 14.And, being provided with and proofreading and correct with air chamber installing mechanism (in Fig. 1, omitting diagram), this correction can releasably be configured on the light path 10 with one in the air chamber proofreading and correct with the air chamber installing mechanism.
The detection signal of photodetector 8 is output in the arithmetic unit 16 that is made of arithmetic processing circuit, special purpose computer or general purpose personal computer.Arithmetic unit 16 possesses the program of calculating the measuring object constituent concentration in the sample air according to the detection signal of photodetector 8.
Can utilize same device to realize control part 6 and arithmetic unit 16, also can utilize different devices to realize control part 6 and arithmetic unit 16.
The Wavelength of Laser that produces from LASER Light Source 2 is being carried out timing, and the detection signal of photodetector 8 also is output to control part 6.
Fig. 2 A at length illustrates near the vertical view of proofreading and correct with the air chamber installing mechanism.In order to utilize the mirror 18 of turning back to make the light path 10 of laser change directions, and utilize condenser 20 that it is carried out optically focused it is guided to photodetector 8 from measuring the laser aiming penetrated with air chamber 12 to photodetector 8.Laser penetrates from LASER Light Source 2, becomes directional light and is directed into air chamber 12 to the optical system of measuring with air chamber 12 incidents by making laser.The state of the laser keeping parallelism light that penetrates from air chamber 12 is directed to condenser 20 from the mirror 18 of turning back, utilize condenser 20 with its optically focused on photodiode 8 as photodetector.Proofread and correct and releasably be installed on the laser optical path 10 with air chamber 14.In this example, can be disposed on the light path of turning back between mirror 18 and the condenser 20 with air chamber 14 proofreading and correct.Design and make not and can make laser produce vignetting (Vignetting) even or cause that the spot position skew or have of laser on photodetector 8 is offset but the output of photodetector 8 also is maybe can proofreading and correct the output of photodetector 8 of fixing owing to proofreading and correct insertion with air chamber 14.Measure with air chamber 12 and proofread and correct disposing with in the light path of air chamber 14, parallel and cause interference for fear of the window of air chamber 12,14, on window with voussoir (Wedge).
Shown in front elevation among Fig. 2 B, as proofread and correct the part that has an opening on top with the supporting device 22 of air chamber installing mechanism make it possible to will proofread and correct with air chamber 14 from above the mode that embeds install to proofread and correct and use air chamber 14, to supporting device 22 position feasible when air chamber 14 is installed on this peristome light path 10 through the central part of air chamber 14.
Fig. 3 schematically shows possesses the situation of a plurality of corrections with air chamber 14a～14d.Among selection air chamber 14a～14d any is installed on the supporting device 22.When not using correction to use air chamber, any among air chamber 14a～14d is not installed on the supporting device 22.
Fig. 4 shows other embodiment that proofreaies and correct with the air chamber installing mechanism.Utilize the turning axle 25 parallel to support air chamber retainer 23 in the mode that can be rotated with the optical axis 10 of laser.Air chamber retainer 23 disposes a through hole 15 and a plurality of correction air chamber 14a～14c on the circumference that is the center of circle with this turning axle 25.By air chamber retainer 23 is rotated, any air chamber among through hole 15 or the air chamber 14a～14c can be configured on the optical axis 10.Carrying out common sample air when measuring, positioning through hole 15 is positioned on the optical axis, when carrying out wavelength calibration or sensitivity correction or the low concentration sample measured, an air chamber of the regulation among air chamber 14a～14c is being configured on the light path 10.
Then, utilize Fig. 5 wavelength calibration to be described to Fig. 9.In order to carry out wavelength calibration, as shown in Figure 5, control part 6 possesses wavelength variation data maintaining part 30, this wavelength variation data maintaining part 30 keeps wavelength variation data, this wavelength variation data representation the drive condition of LASER Light Source 2 is carried out predetermined parameter and the optical maser wavelength that produced between relation.In this example, drive condition being carried out predetermined parameter is the temperature of laser bodies, promptly flows to the current value I t of the Peltier's element of the thermoregulation mechanism 3 be built in laser bodies.The wavelength variation data representation flow to the current value of Peltier's element and the optical maser wavelength that produced between relation.Control part 6 also possesses wavelength variation adjustment of data portion 32, and the wavelength of the absorption peak of this wavelength variation adjustment of data portion 32 based on the light path 10 that wavelength calibration is installed in laser with air chamber the time is proofreaied and correct the wavelength variation data of wavelength variation data maintaining part 30.Control part 6 also possesses the input part 34 that is used to set wavelength, and this wavelength is to be used for wavelength that the measuring object composition is measured.
Below, enclosed methane (CH with the carbon monoxide in the sample air (CO) as measuring object composition, use
4) air chamber and enclosed water vapor (H
2O) air chamber is that example describes as the wavelength calibration air chamber.
When the measuring object composition is measured, the wavelength variation Data Control that control part 6 is kept according to wavelength variation data maintaining part 30 flows to the current value I t of Peltier's element, so that the temperature of laser bodies becomes the temperature of the laser that produces the specific wavelength that is suitable for measure CO.The drive current that offers LASER Light Source 2 from laser drive circuit 4 is when measuring the measuring object composition and carry out timing and all be always fixing reference current Io.
When carrying out wavelength calibration, measure with the sample air that do not circulate in the air chamber 12, and replace with the gas that nitrogen etc. does not comprise the measuring object composition in air chamber 12 in gasmetry.To enclose CH
4Wavelength calibration be configured on the light path 10 with air chamber as proofreading and correct with air chamber, the current value that flows to the Peltier's element of thermoregulation mechanism 3 from control part 6 is controlled so that the temperature of laser bodies changes.Thus, the Wavelength of Laser that produces from LASER Light Source 2 changes and carries out length scanning.By this length scanning, obtain absorption spectrum shown in Figure 6.Such shown in arrow among Fig. 6, CH
4At 4294cm
-1Near have outstanding strong absorption line.Can clearly know the detailed peak wavelength (wave number) of this absorption line.The wavelength variation adjustment of data portion 32 of control part 6 is taken into the temperature of this peak wavelength and the laser bodies of this moment, promptly flows to the current value I t of the Peltier's element of thermoregulation mechanism 3
1As the wavelength variation data.
Then, will enclose H
2The wavelength calibration of O is configured on the light path 10 with air chamber as proofreading and correct with air chamber, equally the current value that flows to the Peltier's element of thermoregulation mechanism 3 from control part 6 is controlled so that the temperature of laser bodies changes.Thus, the Wavelength of Laser that produces from LASER Light Source 2 changes and carries out length scanning, by this length scanning, obtains absorption spectrum shown in Figure 7.Such shown in arrow among Fig. 7, H
2O is at 4270cm
-1Near have outstanding strong absorption line.Can clearly know the detailed peak wavelength (wave number) of this absorption line.The wavelength variation adjustment of data portion 32 of control part 6 is taken into the temperature of this peak wavelength and the laser bodies of this moment, promptly flows to the current value I t of the Peltier's element of thermoregulation mechanism 3
2As the wavelength variation data.
Current value I t when like this, utilizing two kinds of corrections to obtain producing the laser of two wavelength with air chamber
1, It
2As parameter.Wavelength variation adjustment of data portion 32 utilizes these two parameters that the wavelength variation data that wavelength variation data maintaining part 30 is kept are proofreaied and correct.When being illustrated, the wavelength variation data after proofreading and correct obtain Fig. 8.Certainly, also can use the peak wavelength more than three to carry out wavelength calibration.
When according to the wavelength variation data after this correction during from wavelength (wave number) that input part 34 input is used for the measuring object composition is measured, the current value I t of Peltier's element that is flowed to thermoregulation mechanism 3 by control part 6 controls is to obtain being used to producing the laser bodies temperature of the laser of this wavelength.
When the CO as the measuring object composition was described, as shown in Figure 9, CO was from wave number 4270cm
-1To 4300cm
-1Have 9 distinctive absorption lines.Utilize arbitrary concentration that absorbs line can both measure CO gas, but owing near this frequency, also have a lot of CH
4, H
2Therefore the absorption line of O can not be ignored owing to absorb the noise that the interference of line causes, therefore need select the less absorption line of interference effect well.By wavelength (wave number), according to the wavelength variation data after proofreading and correct the Wavelength of Laser that produces from LASER Light Source 2 is controlled by control part 6 from the less absorption line of this interference effect of input part 34 inputs.In addition, can know correctly that also these many which bar that absorbs in the line that use CO absorb line and measure.Like this, by separately use the absorption line of CO according to the gaseous species that has interference effect, interference effect can be limited in Min..
Then sensitivity correction is described with reference to Figure 10 and Figure 11.Sensitivity correction is meant that the inspection amount line data that the absorbance that is used for measuring is transformed to concentration value proofread and correct.When carrying out sensitivity correction, use to enclose the measuring object composition that concentration is different and concentration is known is arranged at least two sensitivity corrections with air chamber as the correction air chamber.As shown in figure 10, arithmetic unit 16 possesses inspection amount line data maintaining part 40 and inspection amount line adjustment of data portion 42, wherein, this inspection amount line data maintaining part 40 is kept for calculating the inspection amount line data of the concentration of measuring object composition, and this inspection amount line adjustment of data portion 42 utilizes the absorbance that obtains when being installed on the laser optical path 10 with air chamber sensitivity correction that the inspection amount line data of inspection amount line data maintaining part 40 are proofreaied and correct.
When carrying out sensitivity correction, will be fixed as the specific wavelength that is used to measure this measuring object composition from the Wavelength of Laser that LASER Light Source 2 produces.When carrying out sensitivity correction, measure with the sample air that do not circulate in the air chamber 12, and replace with the gas that nitrogen etc. does not comprise the measuring object composition in air chamber 12 in gasmetry.Be located at and maintain the inspection amount line data that are expressed as Ao among Figure 11 in the inspection amount line data maintaining part 40.
To be configured in air chamber 14 as sensitivity correction with air chamber with the sensitivity correction that concentration known C1 has enclosed measuring object composition CO and measure absorbance A b on the light path 10
1Then, will be with concentration known C
2The sensitivity correction of having enclosed CO is configured in air chamber 14 as sensitivity correction with air chamber measures absorbance A b on the light path 10
2Inspection amount line adjustment of data portion 42 uses two CO concentration C
1, C
2Following resulting absorbance A b
1, Ab
2Come as A among Figure 11
1Shown in the inspection amount line data that like that inspection amount line data maintaining part 40 kept proofread and correct.Certainly, also can use the different sensitivity correction of concentration more than three to carry out sensitivity correction, can also suppose that inspection amount line utilizes a sensitivity correction to carry out sensitivity correction with air chamber by initial point with air chamber.
When the CO concentration of sample air is measured, sensitivity correction is removed from light path 10 with air chamber 14, sample air is flowed into measure and measure absorbance A b with air chamber 12.The data based measured absorbance A b of inspection amount line that arithmetic unit 16 is used after proofreading and correct calculates concentration.
Explanation improves the mode of signal to noise ratio (S/N ratio) under the situation of using sensitivity correction with the measuring object composition of air chamber 14 measurement low concentrations.In this case, when being measured, sample air also on laser optical path 10, disposes the sensitivity correction air chamber 14 that inclosure has the suitable and known measuring object composition of concentration.The measuring object composition is CO in this case, is sealing into this sensitivity correction and for example is 1ppm with the CO concentration in the air chamber.If measuring the absorbance measuring value of utilizing sensitivity correction to obtain with air chamber 14 with not circulating sample air in the air chamber 12 is Abo.
When configuration sensitivity correction does not make the sample air that circulates in measuring with air chamber 12 measure absorbance with air chamber 14 on light path 10, shown in the Bo of Figure 12, change like that corresponding to the absorbance measuring value of the measuring object constituent concentration in the sample air.According to this measuring method, at the measuring object constituent concentration for having absorbance A b
1Under this situation near 0 low concentration, absorption peak diminishes, and becomes not obvious with the difference of background, because wave length shift and can't carry out concentration determination accurately.
Therewith relatively, when utilizing the manner, be configured in light path 10 on air chamber 14 sensitivity correction and make to measure and circulate sample air when measuring absorbance, even the measuring object constituent concentration is for having absorbance A b with air chamber 12
1Under this situation, also can detect Ab near 0 low concentration
1With the absorbance A b that obtains after the Abo addition
1' therefore as the absorbance measuring value, can not lose absorption peak, and can recently measure with the noise that is enough to carry out correct measurement of concetration.
In this case, as shown in figure 10, arithmetic unit 16 possesses absorbance correction portion 44.Absorbance correction portion 44 is carried out the absorbance A b that obtains from by photodetector 8
1' in deduct the computing of sensitivity correction with the absorbance A bo of air chamber, calculate concentration according to inspection amount line data afterwards.
In the superincumbent explanation, measuring object is become to be divided into CO, with CH
4And H
2O is as the gas of inclosure wavelength calibration with air chamber, but this only is an example, and the present invention also can be applied to other gas certainly.
Claims (9)
1. analytical equipment that is used for the Laser Measurement absorption spectrum possesses:
LASER Light Source, it produces the laser as measuring light, and this measuring light has the specific wavelength that is absorbed by the measuring object composition in the sample gas;
The LASER Light Source driving control device, its control is to the driving of above-mentioned LASER Light Source;
Photodetector, it is disposed at the position that receives above-mentioned laser;
The measurement air chamber of sample air, it is disposed on the light path of the laser from above-mentioned LASER Light Source to above-mentioned photodetector;
Air chamber is used at least one correction, and its inclosure has calibration gas;
Proofread and correct and use the air chamber installing mechanism, it can releasably be disposed at above-mentioned correction on the above-mentioned light path with air chamber with a correction in the air chamber; And
Arithmetic unit, its detection signal according to above-mentioned photodetector is calculated the concentration of the measuring object composition in the sample air.
2. analytical equipment according to claim 1 is characterized in that,
Above-mentioned LASER Light Source is the LASER Light Source that can change wavelength,
Above-mentioned LASER Light Source driving control device possesses wavelength variation data maintaining part, this wavelength variation data maintaining part keeps the wavelength variation data, this wavelength variation data representation the drive condition of above-mentioned LASER Light Source is carried out predetermined parameter and the optical maser wavelength that produced between relation
When the measuring object composition was measured, above-mentioned LASER Light Source driving control device was according to the driving of the wavelength variation Data Control that is kept to above-mentioned LASER Light Source, so that above-mentioned LASER Light Source produces the laser of specific wavelength.
3. analytical equipment according to claim 2 is characterized in that,
The above-mentioned LASER Light Source that can change wavelength possesses the thermoregulation mechanism that the temperature of laser bodies is regulated, and can the optical maser wavelength of generation be changed by the temperature of regulating laser bodies,
Above-mentioned LASER Light Source driving control device provides fixing reference current to the laser bodies that is used for the driving laser light source, provides electric current to the said temperature governor motion of the temperature that is used to regulate laser bodies,
In the time will making the optical maser wavelength that produces from the above-mentioned LASER Light Source that can change wavelength fixedly, the electric current that above-mentioned LASER Light Source drive control device controls provides to above-mentioned thermoregulation mechanism so that the temperature of laser bodies fix, when the optical maser wavelength that will make generation changes, the electric current that above-mentioned LASER Light Source drive control device controls provides to above-mentioned thermoregulation mechanism so that the temperature of laser bodies change.
4. analytical equipment according to claim 3 is characterized in that,
Above-mentioned correction comprises the wavelength calibration air chamber with air chamber, and this wavelength calibration has the long gas of known absorption spike with enclosing in the air chamber to have,
Above-mentioned LASER Light Source driving control device possesses wavelength variation adjustment of data portion, and the absorption peak wavelength of this wavelength variation adjustment of data portion when above-mentioned wavelength calibration is installed on above-mentioned light path with air chamber proofreaied and correct the wavelength variation data that above-mentioned wavelength variation data maintaining part is kept.
5. analytical equipment according to claim 4 is characterized in that,
Above-mentioned wavelength calibration comprises first wavelength calibration air chamber and the second wavelength calibration air chamber with air chamber, this first wavelength calibration is positioned at the long wavelength side longer than above-mentioned specific wavelength with the absorption peak wavelength of the gas of enclosing in the air chamber, and this second wavelength calibration is positioned at the short wavelength side shorter than above-mentioned specific wavelength with the absorption peak wavelength of the gas of enclosing in the air chamber.
6. according to each the described analytical equipment in the claim 1 to 4, it is characterized in that,
Above-mentioned correction comprises at least one sensitivity correction air chamber of having enclosed the measuring object composition that concentration is different and concentration is known with air chamber,
Above-mentioned arithmetic unit possesses: inspection amount line data maintaining part, and it is kept for calculating the inspection amount line data of the concentration of measuring object composition; And inspection amount line adjustment of data portion, it utilizes the absorbance that obtains when above-mentioned sensitivity correction is installed on above-mentioned light path with air chamber that the inspection amount line data that above-mentioned inspection amount line data maintaining part is kept are proofreaied and correct.
7. analytical equipment according to claim 6 is characterized in that,
Above-mentioned sensitivity correction also is configured on the light path of laser when measuring sample air with air chamber,
Above-mentioned arithmetic unit possesses the absorbance correction portion, and this absorbance correction portion deducts the absorbance that the sensitivity correction on utilization is configured in laser when measuring sample air the light path obtains with air chamber from the absorbance of utilizing photodetector to obtain.
8. according to each the described analytical equipment in the claim 1 to 7, it is characterized in that,
Above-mentioned correction is releasably to be installed on supporting device on the above-mentioned light path with proofreading and correct with air chamber with the air chamber installing mechanism.
9. according to each the described analytical equipment in the claim 1 to 8, it is characterized in that,
Above-mentioned correction possesses the air chamber retainer with the air chamber installing mechanism, this air chamber retainer disposes through hole and a plurality of correction air chamber on the circumference that with the rotation center is the center, by this air chamber retainer is rotated through hole or any correction are disposed on the above-mentioned light path with air chamber.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2008/057320 WO2009128138A1 (en) | 2008-04-15 | 2008-04-15 | Gas analyzing apparatus with built-in calibration gas cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102007397A true CN102007397A (en) | 2011-04-06 |
| CN102007397B CN102007397B (en) | 2016-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880128659.8A Expired - Fee Related CN102007397B (en) | 2008-04-15 | 2008-04-15 | It is mounted with the gas analyzing apparatus of correction air chamber |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5360053B2 (en) |
| CN (1) | CN102007397B (en) |
| WO (1) | WO2009128138A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2009128138A1 (en) | 2009-10-22 |
| JPWO2009128138A1 (en) | 2011-08-04 |
| CN102007397B (en) | 2016-08-17 |
| JP5360053B2 (en) | 2013-12-04 |
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