CN105987895B - A kind of laser Raman spectroscopy gas analyzer - Google Patents
A kind of laser Raman spectroscopy gas analyzer Download PDFInfo
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- CN105987895B CN105987895B CN201510097948.8A CN201510097948A CN105987895B CN 105987895 B CN105987895 B CN 105987895B CN 201510097948 A CN201510097948 A CN 201510097948A CN 105987895 B CN105987895 B CN 105987895B
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Abstract
The present invention provides a kind of laser Raman spectroscopy gas analyzer, including laser, optical resonator, hollow reflective pipe, scattering light collecting device and spectrometer；Laser emits laser beam to optical resonator；Optical resonator is made of optical resonance resonant reflec-tors；Hollow reflective Guan Weiyi roots accommodate the hollow pipe of gas to be analyzed, are placed between optical resonator two of which optical resonance resonant reflec-tors, and optical resonance intracavitary laser beam enters from hollow reflective pipe one end, are projected from the other end；Optical resonance intracavitary laser beam generates scattering light in hollow reflective inside pipe wall internal communication, with gas molecule effect to be analyzed in pipe；It scatters light and passes through tube wall multiple reflections inside hollow reflective pipe, projected from hollow reflective pipe both ends.It is long that the instrument using piezoelectric ceramics accurately adjusts optical resonator chamber, locks external incoming laser beam longitudinal mode, intracavitary forms enhancing laser beam；Enhancing effect is tens times or higher of simple optical resonator enhancing technology, improves the sensitivity of detection of gas.
Description
Technical field
The present invention relates to aerochemistry analysis of components and detection field, more particularly to a kind of laser Raman spectroscopy gas analysis
Instrument.
Background technology
Nineteen twenty-eight C.V. Raman experiments find that light passes through transparent medium to be changed by the light occurrence frequency of molecular scattering, this
Phenomenon is known as Raman scattering.In the scattering spectrum of transparent medium, frequency and incident light frequency υ0Identical ingredient is known as Rayleigh
Scattering；Frequency is symmetrically distributed in υ0The spectral line or bands of a spectrum of both sides are Raman spectrum, wherein the smaller ingredient υ of frequency0Δ υ is again
Referred to as stockes line, the larger ingredient υ of frequency0+ Δ υ is also known as anti-stockes line.Due to the number of Raman line, displacement
Size, the length of spectral line is directly related with sample molecule vibration or rotational energy level, and Raman spectrum, which can be distinguished accurately, to be shone
Penetrate the chemical composition of substance.With the appearance of laser after nineteen sixty, high-quality high intensity monochromatic light is provided so that Raman spectrum
It gradually grows up in the application of substance chemical analysis analysis field.
Laser Raman spectroscopy Analysis On Gaseous Constituentss are a kind of technologies developed in recent years.The technology has detection speed
Soon, it samples less, multiple components can be analyzed simultaneously, is small, safeguarding the features such as simple and usage time is long, being very suitable for dividing online
Analysis measures industrial process gas component content.Laser Raman spectroscopy gas analysis technology can be applied to petroleum works gas detection logging,
Natural gas component detects and calorimetry, heat-treating atmosphere control, power plant soot control, the ironmaking of steel plant, steel-making, coking
The coal gas on-line analysis of journey, oil refining process gas-monitoring, the control of fermentation process gas detection, coal chemical industry, chemical fertilizer production, methanol and
The fields such as ethyl alcohol production, fining.
Laser Roman spectroscopic analysis of composition technology is still faced with some challenges in gas analysis field, wherein most important is exactly to draw
Graceful scattered light signal is very faint, and the sensitivity of common laser Raman spectroscopic detection gas is not achieved detection and requires at all, this is just
It needs to improve Raman scattered light intensity by various methods.In patent US4648714, Robert E.Benner are by gas sample
Product box is placed on laser resonator intracavitary, is divided gas to realize using the stronger laser field strength of laser resonance intracavitary
Analysis；Patent EP0557655B1 discloses a kind of method improving scattering light (such as Raman) collection efficiency using hollow reflective pipe, should
Hollow reflective pipe outer wall is coated with high reflectance film layer, and the laser beam of horizontal infection generates Raman with gas effect in pipe and dissipates in pipe
Light is penetrated, Raman diffused light projects after multiple reflections from hollow reflective pipe both ends or center opening；Patent US5521703 is disclosed
A kind of method that hollow reflective tube interior gas Raman signal is excited using semiconductor laser (or making laser diode),
The hollow reflective inside pipe wall plate reflective coating, the laser beam that semiconductor laser is emitted need not in pipe parallel transmission；Specially
Sharp US5432610 discloses a kind of method of diode-end-pumped resonant cavity enhancing chemical gas analysis, resonance cavity reflection
Optical signal feedback is to semiconductor laser, and for the longitudinal mode of semiconductor laser with the locking of resonant cavity longitudinal mode, the interior formation of resonant cavity is stronger
Laser field strength.In document (Analyst, 2012,137,4669), Robert Salter disclose a kind of resonant cavity enhancing
The method of Raman spectrum gas phase analysis, this method equally use laser diode, the difference is that should with patent US5432610
Document feeds back to laser diode using resonant cavity transmitted light, and the longitudinal mode of laser diode is locked with resonant cavity longitudinal mode, resonant cavity
It is interior to form stronger laser field strength.The above technological invention is summarized, the method that two kinds of enhancing Raman scattering signals can be summarized as, i.e.,
Enhance excitation light power and improves scattering light collection efficiency.
Currently, the optimal detection sensitivity that the technological invention of these types enhancing gas Raman scattered signal can reach is
The application requirement of ppb magnitudes is also not achieved in 1ppm, as volatile organic compounds (volatile organic compounds,
VOC it) detects.Therefore seek higher Raman signal enhancing method, be still the focus on research direction of industry.
Invention content
The invention discloses a kind of laser Raman spectroscopy gas analyzer, technical solution is：
A kind of laser Raman spectroscopy gas analyzer, including laser, optical resonator, hollow reflective pipe, scattering light are received
Acquisition means and spectrometer；
Laser emits laser beam to optical resonator；
Optical resonator is made of optical resonance resonant reflec-tors；
Hollow reflective Guan Weiyi roots accommodate the hollow pipe of gas to be analyzed, are placed on optical resonator two of which optics
Between cavity mirror, optical resonance intracavitary laser beam enters from hollow reflective pipe one end, is projected from the other end；Optical resonance
Endovenous laser beam generates scattering light in hollow reflective inside pipe wall internal communication, with gas molecule effect to be analyzed in pipe；Scatter light
Pass through tube wall multiple reflections inside hollow reflective pipe, is projected from hollow reflective pipe both ends.
Preferably, optical resonator is made of two optical resonance resonant reflec-tors.
Preferably, further include piezoelectric ceramics and piezoelectric ceramics electricity for adjusting distance between optical resonance resonant reflec-tors
The piezoelectric ceramic control device of connection, control device include photodetector and piezoelectric ceramics control module；Photodetector is used for
The reflection laser beam or transmission laser beam of optical resonator are received, piezoelectric ceramics is used to adjust optics according to photo detector signal
Spacing between cavity mirror, to lock laser beam longitudinal mode.
Preferably, hollow reflective inside pipe wall is coated with metallic reflection film layer or the optical medium film to Raman scattering light reflection
Layer.
Preferably, hollow reflective tube material itself is transparent to Raman diffused light, and it is anti-that hollow reflective pipe outer wall is coated with metal
Penetrate film layer or the optical medium film layer to Raman scattering light reflection.
Preferably, hollow reflective tube material itself is to Raman scattering light reflection.
Preferably, optical resonator is externally provided with a smooth separator, and the light separator is by laser beam and Raman scattering
Light detaches.
Preferably, light separator is a small size speculum for tilting installation, and size is less than scattering light hot spot ruler
It is very little.
Preferably, light separator is the dichroscope for tilting installation.
Preferably, light separator is slant reflection mirror, is provided with a hole thereon, laser beam passes therethrough.
Preferably, optical resonator is externally provided with a concave mirror, and scattering light is reflected back hollow anti-through concave mirror
It penetrates inside pipe.
Preferably, between collecting the opposite hollow reflective pipe end and adjacent optical cavity mirror in one end with scattering light
If there are one concave mirrors, it is provided with a hole thereon, optical resonance intracavitary laser beam passes therethrough, and scattering light is through concave reflection
Mirror is reflected back inside hollow reflective pipe.
Preferably, between collecting the opposite hollow reflective pipe end and adjacent optical cavity mirror in one end with scattering light
If there are one sliders, it is provided with a hole thereon, optical resonance intracavitary laser beam passes therethrough, and slider can prevent air stream contamination
Optical resonance resonant reflec-tors.
Preferably, a slant reflection mirror is equipped between hollow reflective pipe one end and adjacent optical cavity mirror,
On be provided with a hole, optical resonance intracavitary laser beam is passed through from hole；The scattering light being emitted from hollow reflective pipe is through slant reflection mirror
After reflection, is detached with laser optical path and be input to scattering light collecting device.
Preferably, a slant reflection mirror is equipped between the hollow reflective pipe other end and adjacent optical cavity mirror,
It is provided with a hole thereon, optical resonance intracavitary laser beam is passed through from hole；The scattering light being emitted from hollow reflective pipe is through slant reflection
After mirror reflection, is detached with laser optical path and be input to scattering light collecting device.
Preferably, concave reflection there are one being set between the hollow reflective pipe other end and adjacent optical cavity mirror
Mirror is provided with a hole thereon, and optical resonance intracavitary laser beam passes therethrough, and scattering light is reflected back hollow reflective through concave mirror
Inside pipe.
Preferably, it is set between the hollow reflective pipe other end and adjacent optical cavity mirror there are one slider,
On be provided with a hole, optical resonance intracavitary laser beam passes therethrough, and slider can prevent air stream contamination optical resonance resonant reflec-tors.
Preferably, gas analyzer further includes gas sample room, and optical resonator and hollow reflective pipe are located at gas sample
This interior；Gas sample room is equipped with air inlet pipe and an air outlet pipe；Gas to be analyzed enters the gas sample room by air inlet pipe, from hollow
It flows through inside reflection tube, is flowed out by escape pipe.
Preferably, gas sample chamber is equipped at least one optical window；The scattering light being emitted from hollow reflective pipe is through oblique
After the speculum reflection of face, projected from optical window.
Preferably, a Faraday isolator is equipped between laser and optical resonator.
Preferably, a bandpass filter is equipped between laser and optical resonator.
Preferably, a short wave pass filter is equipped between laser and optical resonator.
Preferably, a laser beam enlarging bind device is equipped between laser and optical resonator.
Preferably, a laser beam attenuator is equipped between laser and optical resonator.
Preferably, it scatters and is equipped with a long wave pass filter in light collecting device.
Preferably, it scatters and is equipped with a notch filtering light piece in light collecting device.
Preferably, scattering light collecting device connects spectrometer by fiber optic bundle.
Preferably, 2 scattering light collecting devices are equipped with, is respectively used to receive backward Raman scattering and forward direction Raman dissipates
It penetrates.
Preferably, fiber optic bundle output end inner fiber is arranged in a row.
Preferably, modulus (A/D) converter and digital-to-analogue (D/A) converter are equipped in piezoelectric ceramics control module.
Preferably, a voltage amplification module is equipped in piezoelectric ceramics control module.
Preferably, a central processing unit (CPU) is equipped in piezoelectric ceramics control module.
Preferably, optical resonator is made of three or four optical resonance resonant reflec-tors.
Accurately adjustment optical resonator chamber is long for piezoelectric ceramics (PZT), makes optical resonator locked laser longitudinal mode, laser
The laser beam exported is coupled to optical resonance intracavitary, and optical resonance intracavitary is formed compared with light laser light beam.In optical resonator
It is placed in parallel a hollow reflective pipe, is charged with gas to be analyzed.The internal diameter of the hollow reflective pipe is more than optical resonance intracavitary
The diameter of laser beam, can make the laser beam in optical resonator inside hollow reflective inside pipe wall Free propagation without touching
Tube wall；Optical resonance intracavitary laser beam generates Raman diffused light with the detected gas effect inside hollow reflective pipe；Due to sky
The inner wall or outer wall of oculo cardiac reflex pipe are coated with the film layer to Raman diffused light high reflection, and Raman diffused light passes through in hollow reflective pipe
Multiple reflections, last Raman diffused light are exported from hollow reflective pipe both ends；The Raman diffused light that hollow reflective pipe both ends are exported
It can be input in spectrometer by optical receiver assembly, finally obtain the Raman spectrum of gas.
The present invention compared with invention difference lies in：1. in patent US4648714, gaseous sample box (non-hollow reflective pipe)
It is placed on laser resonator intracavitary；Another light is placed on using a hollow reflective pipe filled with gas to be analyzed in the present invention
It learns in resonant cavity, the optical resonator is in laser external.2. hollow in patent EP0557655B1 and patent US5521703
Reflection tube is located at laser external, resonant cavity is not used to enhance laser beam；Hollow reflective pipe is located in the present invention
Optical resonance intracavitary, using optical resonator enhances laser beam.3. in patent US5432610 and document
In (Analyst, 2012,137,4669), reflected light and transmitted light that optical resonator has been respectively adopted are fed back as feedback light
To inside laser diode, the longitudinal mode of semiconductor laser is made to be locked with external optical resonant cavity longitudinal mode；It uses in the present invention
Accurately adjustment optical resonator chamber is long for piezoelectric ceramics (PZT), makes optical resonator locked laser longitudinal mode；In addition, the present invention adopts
It is placed on optical resonance intracavitary with a hollow reflective pipe filled with gas to be analyzed.
Existing invention is compared, the method have the benefit that：1. can be placed between laser and optical resonator
Optical filter can effectively filter out the veiling glare spectrum that laser is sent out such as laser rays bandpass filter.2. can be in laser output work
In the case of rate is identical, the laser beam power of same gas effect is increased considerably using optical resonator, thus can be generated more
Strong Raman diffused light.3. external feedback light is not present, laser works independently, and stability improves；Hollow reflective pipe can be carried effectively
Height scattering light collection efficiency.
Description of the drawings
Fig. 1 is the laser Raman spectroscopy gas analyzer using back scattering collection mode；
Fig. 2 is 1 structural schematic diagram of laser module；
Fig. 3 is a kind of realization method of gas sample room 4；
Fig. 4 is 21 schematic diagram of hollow reflective pipe；
Fig. 5, which is chamber, enhances laser beam in hollow reflective pipe internal communication schematic diagram；
Fig. 6 a are that hollow reflective inside pipe wall scatters light collection efficiency schematic diagram to scattering light reflection to enhance；
Fig. 6 b are that hollow reflective pipe outer wall scatters light collection efficiency schematic diagram to scattering light reflection to enhance；
Fig. 7 is a kind of realization method of piezoelectric ceramics control module 7；
Fig. 8 is Raman scattering light collecting system schematic diagram；
Fig. 9 is a kind of realization method that optical resonator enhances technology；
Figure 10 is the laser Raman spectroscopy gas analyzer using forward scattering collection mode；
Several realization methods of Figure 11 a-11c gas samples room 4；
Figure 12 is a kind of laser Raman spectroscopy gas analyzer；
Figure 13 a-13b are 36 schematic diagram of slant reflection mirror；
Figure 14 is 37 schematic diagram of concave mirror；
Figure 15 is a kind of gas sample room 4；
Figure 16 is a kind of preceding to-backward Raman scattering light collecting system schematic diagram；
Figure 17 a-17b are relationship of the optical resonator between the transmitance T of laser beam, reflectivity R and light path (nL)
Specific implementation mode
In order to understand the present invention in depth, with reference to specific embodiment and attached drawing, the present invention is described in detail.
Embodiment one
Attached drawing 1 is a kind of laser Raman spectroscopy gas using back scattering collection mode that the embodiment of the present invention one provides
Analyzer, including laser module 1, small size speculum 3, gas sample room 4, photodetector 5, piezoelectric ceramics control module 7,
Scatter light collecting device 10, fiber optic bundle 11 and spectrometer 12.
Wherein, referring to attached drawing 2, swash as a kind of specific implementation of laser module 7, including laser 13, faraday
Optoisolator 14, bandpass filter 15, lens 16, small filter 17 and lens 18.Laser 13 emits laser beam 2a, can be with
Using any one laser, such as gas laser, semiconductor laser, solid-state laser, use in the present embodiment
One semiconductor pumped solid (DPSS) single longitudinal mode green laser, outgoing laser beam are single longitudinal mode, wavelength Xlaser=
532nm；Faraday's laser isolator 14 avoids reflected light return laser light device for subsequent optical element reflected light to be isolated；Band logical
Optical filter 15 is 532nm through wavelength, laser center wavelength can be made to pass through, and completely cuts off the veiling glare of other wavelength, avoids veiling glare
Into subsequent optical element；Lens 16 and lens 18 form a telescope, are expanded for laser beam 2a so that shoot laser beam
2b transverse modes are matched with the transverse mode formula of optical resonator.
Wherein, referring to attached drawing 3~6, as a kind of specific implementation of gas sample room 4, including (optical resonator)
Speculum 19, (optical resonator) speculum 20, hollow reflective pipe 21, supporter 23, (optical resonator) cavity 22, piezoelectricity pottery
Porcelain 24, speculum fixed seat 25, air inlet pipe 26 and escape pipe 27.Speculum 19, speculum 20, cavity 22,24 and of piezoelectric ceramics
Speculum fixed seat 25 constitutes a confining gas sample room 4；Speculum 19 and speculum 20 are placed in parallel in gas sample room 4
Both ends；Speculum 20 is fixed in speculum fixed seat 25；Speculum fixed seat 25 is connected to cavity 22 by piezoelectric ceramics 24；It is empty
Oculo cardiac reflex pipe 21 is placed horizontally between speculum 19 and speculum 20, and is connected and fixed on cavity 22 by supporter 23；Quilt
Detection gas enter the gas sample room by air inlet pipe 26, and due to the isolation of supporter 23, detected gas can only be by hollow
Reflection tube 21 flows to escape pipe 27 (gas flowing path is shown in block arrow in Fig. 3)；
The reflecting surface S19 and reflecting surface S20 of speculum 19 and speculum 20 (close to the side of hollow reflective pipe 21, such as scheme
5) it is coated with the film layer reflected laser light wave height respectively, constitutes an optical resonator (optical resonant cavity).
In the present embodiment, S19 and S20 be concave surface, radius of curvature is 200mm, and wherein in the heart away from also be 200mm, thus constitute
One confocal cavity；Laser beam 2b forms laser beam 2c by back and forth being propagated in the optical resonance intracavitary after speculum 19.
Piezoelectric ceramics 24 can be in 8 times generation microdisplacements of Piezoelectric Ceramic voltage, and effect is anti-for accurately adjusting
Penetrate the spacing L between mirror 19 and speculum 20.According to optical resonator theory, inside the optical resonator existing for light wave fields it is vertical
Mould (frequencyv) relationship between spacing L is：
λ/2 nL=m
Wherein nL is the light path that resonance intracavity beam passes through gas, and n is gas refracting index, and c is the light velocity in vacuum, and m is
Integer, λ (λ=c/v) are the wavelength corresponding to resonant cavity longitudinal mode.It therefore, can be with by adjusting optical resonance resonant reflec-tors spacing L
Optical resonator longitudinal mode is set to match (single longitudinal mode v with external incoming laser beam longitudinal modelaser, wavelength Xlaser=532nm), the adjustment
Process is optical resonator locking laser beam longitudinal mode process.It is matched with external incoming laser beam longitudinal mode in optical resonator longitudinal mode
When, from analyzing above：
NL=m λ1aser/2
Figure 17 a are relationship of the optical resonator between the transmitance T and light path (nL) of laser beam, when light path (nL) is sharp
When the integral multiple of light light wave half-wavelength, transmitted light intensity is in maximal peak position, therefore available transmitted light beam signal strength feedback
The spacing L between speculum 19 and speculum 20 is controlled, optical resonator is made to lock laser beam longitudinal mode；Figure 17 b are optical resonance
Relationship of the chamber between the reflectivity R and light path (nL) of laser beam, it is seen that when the integer that light path (nL) is laser light wave half-wavelength
Times when, reflective light intensity is in minimum valley position, therefore equally available reflected light beam signal intensity feedback controls 19 He of speculum
Spacing L between speculum 20 makes optical resonator lock laser beam longitudinal mode.In the present embodiment, using transmitted light beam signal
Feedback-controlled optics resonant cavity locks laser beam longitudinal mode.
According to optical resonator theory, when optical resonator locks laser beam longitudinal mode, laser beam 2c is in the resonant cavity
Standing wave is formed, endovenous laser beam 2c energy is enhanced.During practical mode locking, due to laser power fluctuation, feedback control
The influences such as response speed, control circuit noise and piezoelectric ceramics displacement accuracy, optical resonator longitudinal mode cannot be matched accurately completely
That is, there is longitudinal mode matching error in external incoming laser beam longitudinal mode, but actually since longitudinal mode has certain width, longitudinal mode matching
Error influences endovenous laser beam energy enhancing effect little.
For common lasers, outgoing laser beam is generally more longitudinal modes, and longitudinal mode spacing (i.e. frequency interval) is：
Wherein n ' LlaserFor the light path of laser internal resonance chamber, n ' is the refractive index of laser resonator interior media；Together
Sample, external optical resonant cavity longitudinal mode spacing are：
Therefore, if adjusting the spacing L between speculum 19 and speculum 20, meet nL=q (n ' Llaser) relationship, wherein
Q is integer, i.e., laser beam longitudinal mode spacing is the integral multiple of optical resonator longitudinal mode spacing, can make optical resonator locking all
Laser beam longitudinal mode；The case where being non-integer for q, can only be such that optical resonator lock part laser beam longitudinal mode or locking zero swashs
Light beam longitudinal mode.In short, for common Multi-Longitudinal Mode laser, it can adjust optical resonator and lock at least one laser beam longitudinal mode.
Hollow reflective pipe 21 is a hollow pipe, referring to attached drawing 4, internal diameter size DHW=1mm is more than optical resonance
Endovenous laser spot size DLaser=0.37mm (centered on intensity 1/e2Spot diameter)；Hollow reflective pipe 21 is parallel to laser
The direction of propagation is positioned over the optical resonance intracavitary that speculum 19 and speculum 20 are constituted, and center axis is the same as in laser beam 2c
Mandrel line overlaps, referring to attached drawing 5.Therefore, laser beam 2c enters from hollow reflective pipe one end, is projected from the other end, hollow anti-
Pars intramuralis straightline propagation in pipe 21 is penetrated, 21 inner wall of hollow reflective pipe will not be touched, Free propagation state is in, ensure that relatively low
Laser energy loss late, referring to attached drawing 5.
Laser beam 2c makees in the reciprocal communication process in 21 inside of hollow reflective pipe with the gas molecule full of hollow reflective pipe
Light 9 is scattered with generating, including Rayleigh scattering light and Raman diffused light etc..In the present embodiment one, hollow reflective pipe 21 is
Quartz glass tube, inner wall are coated with the silverskin to scattering light high reflection, and benefit is：It can effectively prevent scattering light 9 to free sky
Between dissipate so that the scattering light generated inside hollow reflective pipe is exported after multiple reflections by hollow reflective pipe both ends, therefore
The collection efficiency for significantly enhancing scattering light, referring to attached drawing 6a.Realization method as hollow reflective pipe 21 includes：1. hollow
Tube wall is coated with metallic diaphragm or optical medium film layer to scattering light reflection.2. being coated in the outer wall of transparent glass tube to dissipating
The metallic diaphragm or optical medium film layer of light reflection are penetrated, as shown in Figure 6 b；3. hollow pipe material itself is to scattering light reflection, such as
Silver pipe.
Wherein, referring to attached drawing 6, the exit direction of scattering light 9a is with the directions incoming laser beam 2b on the contrary, referred to as back scattering
Light；The exit direction for scattering light 9b is identical with the directions incoming laser beam 2b, referred to as forward scattering light.
Wherein, referring to attached drawing 7, as a kind of specific implementation of piezoelectric ceramics control module 7, including signal acquisition with
Processing module 28, piezoelectric ceramic actuator 30.Signal acquiring and processing module 28 is equipped with modulus (A/D) converter, cpu chip
With digital-to-analogue (D/A) converter, modulus (A/D) converter receives the output signal 6 of photodetector 5, and CPU is to collected number
Signal carries out calculation processing；CPU exports digital quantity voltage signal to digital-to-analogue (D/A) converter, and digital-to-analogue (D/A) converter will simulate
Voltage signal 29 is output in piezoelectric ceramic actuator 30；Piezoelectric ceramic actuator 30 is a voltage amplification module, and output is
Piezoelectric Ceramic voltage 8, in this embodiment, the voltage amplification factor of piezoelectric ceramic actuator 30 is 60 times.
Wherein, referring to attached drawing 8, as a kind of specific implementation of scattering light collecting device 10, including lens 31, optical filtering
Piece 32 and lens 33.Lens 31 are for collimating scattering light；Optical filter 32 is for completely cutting off veiling glare composition, such as Rayleigh scattering in scattering light
Light, to Raman scattering light transmission；Lens 33 are for converging to Raman scattering optical signal in fiber optic bundle 11.Lens 31 and lens
33 one imaging optical path of composition, imaging object are the end faces of hollow reflective pipe 21, and imaging magnification depends on two lens cokes
The ratio between away from, i.e. f33:f31；The f in the present embodiment one33=f31, magnifying power 1, therefore scatter light 9 and obtained by the imaging optical path
Picture, i.e. Raman signal hot spot, size be identical with 21 internal diameter size of hollow reflective pipe.In the present embodiment one, hollow reflective
21 internal diameter of pipe is 1mm, so Raman signal spot diameter is 1mm.
Wherein, as a kind of specific implementation of fiber optic bundle 11, the receiving terminal 11a of fiber optic bundle is circle, a diameter of
1mm, wherein containing 7 optical fiber, a diameter of 0.32mm of simple optical fiber；Fiber optic bundle output end 11b is rectangle, and size is
0.32mm × 2.5mm, wherein 7 optical fiber are arranged in a row.It is using effective purpose of this fiber bundle structure parameter：1. fiber optic bundle
Receiving terminal 11a can efficient reception Raman scattering hot spot (its diameter is similarly 1mm).2. reduce the width of 11 output end of fiber optic bundle,
Therefore it can increase the spectrally resolved ability of spectrometer 12.
The overall workflow of the embodiment of the present invention one is：Laser module 1 emits laser beam 2b, and laser beam 2b is through too small ruler
The reflection of very little speculum 3 is input to gas sample room 4；Gas sample room 4 includes an optical resonator (by speculum 19 and reflection
Mirror 20 forms) and a hollow reflective pipe 21；Detected gas flows into hollow reflective pipe 21 by air inlet pipe 26.Laser beam 2d is penetrated
Optical resonator is received by photodetector 5.Photodetector 5, piezoelectric ceramics control module 7 and piezoelectric ceramics 24 constitute one
A resonant cavity clamping system, control optical resonator lock laser beam longitudinal mode.Laser beam 2c forms standing wave in optical resonance intracavitary,
Laser beam energy is enhanced；High energy laser beam acts on gas molecule in 21 internal communication of hollow reflective pipe and generates scattering
Light 9；The scattering light passes through 21 inner wall multiple reflections of hollow reflective pipe, is exported by hollow reflective pipe both ends.Wherein, rear orientation light
After 9a is by speculum 19, by passing through around small size speculum 3, it is input in scattering light collecting device 10；Light is scattered to receive
Raman diffused light convergence is input in fiber optic bundle 11 by acquisition means 10；Fiber optic bundle 11 is connected with spectrometer 12, finally by spectrometer
Analysis obtains the Raman spectrum for being measured gas.
In the present embodiment one, scatter what setting between light collecting device 10 and gas sample room 4 was placed there are one 45 degree
Small size speculum 3, effect are to realize that laser input light path collects light path separation with rear orientation light.
Enhance a kind of realization of Raman spectroscopy referring to attached drawing 9 for optical resonator as the comparison of the present embodiment one
Mode.In intra resonant cavity, laser beam is on propagation path and gas effect generates Raman diffused light, but scatters light and collect dress
10 are set to be only capable of collecting the optical signal on the paths length about 1mm.
In the present embodiment one, using two ways enhances Raman scattering：1. optical resonator is to laser energy
The enhancing of amount.2. enhancing of the hollow reflective pipe 21 to Raman scattering light collection efficiency.The length of hollow reflective pipe 21 is 175mm,
Therefore generated Raman signal can be collected into the length paths, about 175 times of intensification factor.
Embodiment two
Attached drawing 10 is a kind of laser Raman spectroscopy gas using forward scattering collection mode provided by Embodiment 2 of the present invention
Body analyzer, including laser module 1, speculum 35, gas sample room 4, photodetector 5, piezoelectric ceramics control module 7, two
To Look mirror 34, scattering light collecting device 10, fiber optic bundle 11 and spectrometer 12.
The embodiment of the present invention two and embodiment one difference lies in：1. in embodiment two, collected signal is preceding to scattered
Penetrate light 9b.Dichroscope 34 is collected light path for realizing forward direction Raman diffused light and is detached with shoot laser beam 2d；The dichroscope
For a short-pass dichroscope, optical maser wavelength is penetrated, to Raman scattering light reflection.2. in embodiment two, using laser
Beam reflected light signal feedback-controlled optics resonant cavity locks laser beam longitudinal mode.One is equipped between laser module 1 and gas sample room 4
The speculum 35 (reflectivity 1%, transmissivity 99%) of a 45 degree of placements；The laser beam 2e warps reflected from optical resonator
The reflection of speculum 35 is crossed, is finally received by photodetector 5.
The overall workflow of the embodiment of the present invention two is：Laser module 1 emits laser beam 2b, and laser beam 2b is through reflection
It is input to gas sample room 4 after mirror 35；Gas sample room 4 includes an optical resonator (by speculum 19 and speculum 20
Composition) and a hollow reflective pipe 21；Detected gas flows into hollow reflective pipe 21 by air inlet pipe 26.Laser beam 2e is humorous by optics
It shakes and cavity reflection and is returned by original route, then reflected by speculum 35, finally received by photodetector 5.Photodetector 5, pressure
Electroceramics control module 7 and piezoelectric ceramics 24 constitute a resonant cavity clamping system, and control optical resonator locking laser beam is vertical
Mould.Laser beam 2c forms standing wave in optical resonance intracavitary, and laser beam energy is enhanced；High energy laser beam is in hollow reflective pipe
21 internal communications act on gas molecule and generate scattering light 9；The scattering light passes through 21 inner wall multiple reflections of hollow reflective pipe, by
Hollow reflective pipe both ends export.Wherein, it after forward direction Raman diffused light is by speculum 20, is reflected by dichroscope 34, it is last defeated
Enter into scattering light collecting device 10；Raman diffused light convergence is input in fiber optic bundle 11 by scattering light collecting device 10；Optical fiber
Beam 11 is connected with spectrometer 12, and the Raman spectrum for being measured gas is finally obtained by spectrometer analysis.
Embodiment three
Attached drawing 11a is a kind of gas sample room 4 that the embodiment of the present invention three provides, the embodiment of the present invention three and embodiment one
Difference lies in：
1. in embodiment three, a slant reflection mirror 36 is equipped between speculum 19 and hollow reflective pipe 21, center is set
There is an aperture (diameter D36=1mm), laser beam 2c can be from wherein passing freely through；Figure 13 a are 36 schematic diagram of slant reflection mirror, wherein
S36 is reflecting surface；S36 is tilted relative to laser beam 2c；Slant reflection mirror 36 detaches for realizing scattering light 9 with laser beam 2c.
The reflecting surface S36 of slant reflection mirror 36 can also be curved surface, and as shown in Figure 11 b and Figure 13 b, what is be emitted from hollow reflective pipe 21 dissipates
Light 9 is penetrated after the reflection of slant reflection mirror 36, becomes collimated light.
2. cavity 22 is equipped with an optical window 38, the scattering light 9 being emitted from hollow reflective pipe 21 is through slant reflection mirror 36
After reflection, projected by optical window 38.
3. being equipped with a concave mirror 37 between speculum 20 and hollow reflective pipe 21, center is equipped with an aperture (diameter
D37=1mm), laser beam 2c can be from wherein passing freely through.Figure 14 is 37 schematic diagram of concave mirror, and wherein reflecting surface S37 is song
Face, at 21 right end face of hollow reflective pipe, effective benefit is the center of curvature：The forward direction being emitted from hollow reflective pipe 21 dissipates
Light 9b is penetrated after the reflection of concave mirror 37, is returned in hollow reflective pipe 21, last forward scattering light 9b and rear orientation light
9a is projected from 21 left end face of hollow reflective pipe together, therefore enhances the scattering light that 21 left end face of hollow reflective pipe is exported
9 signal strengths.
In the present embodiment three, another effective benefit of slant reflection mirror 36 and concave mirror 37 is：Prevent air-flow
It is diffused on (optical resonator) speculum 19 and (optical resonator) speculum 20, it is humorous to optics to reduce suspended particulate in gas
It shakes the pollutions of resonant reflec-tors.Gas flowing path is shown in attached drawing 11 shown in block arrow.To prevent air stream contamination (optical resonator)
A slider 39 equally can be also arranged in speculum between hollow reflective pipe and (optical resonator) speculum, and center is set
There is an aperture (diameter D37=1mm), laser beam 2c can be from wherein passing freely through, as shown in fig. 11c.
Attached drawing 12 is a kind of laser Raman spectroscopy gas analyzer that the embodiment of the present invention three provides, the embodiment of the present invention three
With embodiment one difference lies in：Laser module 1 emits laser beam 2b and is directly inputted in gas sample room 4；It scatters light and collects dress
It sets 10 and is located at 4 side of gas sample room, for collecting the scattering light 9 being emitted from optical window 38.
Example IV
Attached drawing 15 is a kind of gas sample room 4 that the embodiment of the present invention four provides, the embodiment of the present invention four and embodiment three
Difference lies in：1. setting, there are two slant reflection mirrors 36, and one between speculum 19 and hollow reflective pipe 21；Another is located at
Between speculum 20 and hollow reflective pipe 21.2. being set on cavity 22, there are two optical windows 38, are located at 22 both sides of cavity.
The rear orientation light 9a and forward scattering light 9b projected from 21 both ends of hollow reflective pipe, by the two slant reflections
Mirror 36 reflects, and is projected respectively from two optical windows 38.Attached drawing 16 is to be dissipated to-backward Raman before one kind that the present embodiment four provides
Light collecting system is penetrated, is provided with two scattering light collecting devices 10 and respectively with two fiber optic bundles 11 of its connection；Same spectrum
One end 11c that instrument 12 connects, two fiber optic bundle 11 (containing 7 optical fiber) piece fiber optic bundles of synthesis, all 14 optical fiber arrange together
It is in a row.
Claims (32)
1. a kind of laser Raman spectroscopy gas analyzer, which is characterized in that including laser, optical resonator, hollow reflective pipe,
Scatter light collecting device and spectrometer；
Laser emits laser beam to optical resonator；
Optical resonator is made of optical resonance resonant reflec-tors；
Hollow reflective Guan Weiyi roots accommodate the hollow pipe of gas to be analyzed, are placed on two optical resonators in optical resonator
Between speculum, optical resonance intracavitary laser beam enters from hollow reflective pipe one end, is projected from the other end；Optical resonance intracavitary swashs
Light beam generates scattering light in hollow reflective inside pipe wall internal communication, with gas molecule effect to be analyzed in pipe；Light is scattered hollow
Pass through tube wall multiple reflections inside reflection tube, is projected from hollow reflective pipe both ends；
It is equipped with a slant reflection mirror between hollow reflective pipe one end and adjacent optical cavity mirror, is provided with one thereon
Hole, optical resonance intracavitary laser beam are passed through from hole；The scattering light being emitted from hollow reflective pipe is after the reflection of slant reflection mirror, together
Laser optical path detaches and is input to scattering light collecting device；
Concave mirror there are one being set between the hollow reflective pipe other end and adjacent optical cavity mirror, is provided with thereon
One hole, optical resonance intracavitary laser beam pass therethrough, and scattering light is reflected back through concave mirror inside hollow reflective pipe.
2. a kind of laser Raman spectroscopy gas analyzer, which is characterized in that including laser, optical resonator, hollow reflective pipe,
Scatter light collecting device and spectrometer；
Laser emits laser beam to optical resonator；
Optical resonator is made of optical resonance resonant reflec-tors；
Hollow reflective Guan Weiyi roots accommodate the hollow pipe of gas to be analyzed, are placed on two optical resonators in optical resonator
Between speculum, optical resonance intracavitary laser beam enters from hollow reflective pipe one end, is projected from the other end；Optical resonance intracavitary swashs
Light beam generates scattering light in hollow reflective inside pipe wall internal communication, with gas molecule effect to be analyzed in pipe；Light is scattered hollow
Pass through tube wall multiple reflections inside reflection tube, is projected from hollow reflective pipe both ends；
It is equipped with a slant reflection mirror between hollow reflective pipe one end and adjacent optical cavity mirror, is provided with one thereon
Hole, optical resonance intracavitary laser beam are passed through from hole；The scattering light being emitted from hollow reflective pipe is after the reflection of slant reflection mirror, together
Laser optical path detaches and is input to scattering light collecting device；
It is equipped with a slant reflection mirror between the hollow reflective pipe other end and adjacent optical cavity mirror, is provided with one thereon
Hole, optical resonance intracavitary laser beam are passed through from hole；The scattering light being emitted from hollow reflective pipe is after the reflection of slant reflection mirror, together
Laser optical path detaches and is input to scattering light collecting device.
3. a kind of laser Raman spectroscopy gas analyzer, which is characterized in that including laser, optical resonator, hollow reflective pipe,
Scatter light collecting device and spectrometer；
Laser emits laser beam to optical resonator；
Optical resonator is made of optical resonance resonant reflec-tors；
Hollow reflective Guan Weiyi roots accommodate the hollow pipe of gas to be analyzed, are placed on two optical resonators in optical resonator
Between speculum, optical resonance intracavitary laser beam enters from hollow reflective pipe one end, is projected from the other end；Optical resonance intracavitary swashs
Light beam generates scattering light in hollow reflective inside pipe wall internal communication, with gas molecule effect to be analyzed in pipe；Light is scattered hollow
Pass through tube wall multiple reflections inside reflection tube, is projected from hollow reflective pipe both ends；
It is equipped with a slant reflection mirror between hollow reflective pipe one end and adjacent optical cavity mirror, is provided with one thereon
Hole, optical resonance intracavitary laser beam are passed through from hole；The scattering light being emitted from hollow reflective pipe is after the reflection of slant reflection mirror, together
Laser optical path detaches and is input to scattering light collecting device；
Slider there are one being set between the hollow reflective pipe other end and adjacent optical cavity mirror, is provided with one thereon
Hole, optical resonance intracavitary laser beam pass therethrough, and slider can prevent air stream contamination optical resonance resonant reflec-tors.
4. laser Raman spectroscopy gas analyzer as described in claim 1, which is characterized in that the optical resonator is by two
Optical resonance resonant reflec-tors are constituted.
5. laser Raman spectroscopy gas analyzer as claimed in claim 2, which is characterized in that the optical resonator is by two
Optical resonance resonant reflec-tors are constituted.
6. laser Raman spectroscopy gas analyzer as claimed in claim 3, which is characterized in that the optical resonator is by two
Optical resonance resonant reflec-tors are constituted.
7. laser Raman spectroscopy gas analyzer as described in claim 1, which is characterized in that the gas analyzer further includes
Piezoelectric ceramic control device for adjusting the piezoelectric ceramics and piezoelectric ceramics Electricity Federation of distance between optical resonance resonant reflec-tors, control
Device processed includes photodetector and piezoelectric ceramics control module；Photodetector is used to receive the reflection laser of optical resonator
Beam or transmission laser beam, piezoelectric ceramics be used for according to photo detector signal adjust optical resonance resonant reflec-tors between spacing, from
And lock laser beam longitudinal mode.
8. laser Raman spectroscopy gas analyzer as claimed in claim 2, which is characterized in that the gas analyzer further includes
Piezoelectric ceramic control device for adjusting the piezoelectric ceramics and piezoelectric ceramics Electricity Federation of distance between optical resonance resonant reflec-tors, control
Device processed includes photodetector and piezoelectric ceramics control module；Photodetector is used to receive the reflection laser of optical resonator
Beam or transmission laser beam, piezoelectric ceramics be used for according to photo detector signal adjust optical resonance resonant reflec-tors between spacing, from
And lock laser beam longitudinal mode.
9. laser Raman spectroscopy gas analyzer as claimed in claim 3, which is characterized in that the gas analyzer further includes
Piezoelectric ceramic control device for adjusting the piezoelectric ceramics and piezoelectric ceramics Electricity Federation of distance between optical resonance resonant reflec-tors, control
Device processed includes photodetector and piezoelectric ceramics control module；Photodetector is used to receive the reflection laser of optical resonator
Beam or transmission laser beam, piezoelectric ceramics be used for according to photo detector signal adjust optical resonance resonant reflec-tors between spacing, from
And lock laser beam longitudinal mode.
10. laser Raman spectroscopy gas analyzer as claimed in claim 4, which is characterized in that the gas analyzer also wraps
The piezoelectric ceramic control device for adjusting the piezoelectric ceramics and piezoelectric ceramics Electricity Federation of distance between optical resonance resonant reflec-tors is included,
Control device includes photodetector and piezoelectric ceramics control module；The reflection that photodetector is used to receive optical resonator swashs
Light beam or transmission laser beam, piezoelectric ceramics are used for according to spacing between photo detector signal adjustment optical resonance resonant reflec-tors,
To lock laser beam longitudinal mode.
11. laser Raman spectroscopy gas analyzer as claimed in claim 5, which is characterized in that the gas analyzer also wraps
The piezoelectric ceramic control device for adjusting the piezoelectric ceramics and piezoelectric ceramics Electricity Federation of distance between optical resonance resonant reflec-tors is included,
Control device includes photodetector and piezoelectric ceramics control module；The reflection that photodetector is used to receive optical resonator swashs
Light beam or transmission laser beam, piezoelectric ceramics are used for according to spacing between photo detector signal adjustment optical resonance resonant reflec-tors,
To lock laser beam longitudinal mode.
12. laser Raman spectroscopy gas analyzer as claimed in claim 6, which is characterized in that the gas analyzer also wraps
The piezoelectric ceramic control device for adjusting the piezoelectric ceramics and piezoelectric ceramics Electricity Federation of distance between optical resonance resonant reflec-tors is included,
Control device includes photodetector and piezoelectric ceramics control module；The reflection that photodetector is used to receive optical resonator swashs
Light beam or transmission laser beam, piezoelectric ceramics are used for according to spacing between photo detector signal adjustment optical resonance resonant reflec-tors,
To lock laser beam longitudinal mode.
13. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the hollow reflective
Inside pipe wall is coated with metallic reflection film layer or the optical medium film layer to Raman scattering light reflection.
14. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the hollow reflective
Tube material itself is transparent to Raman diffused light, and hollow reflective pipe outer wall is coated with metallic reflection film layer or to Raman scattering light reflection
Optical medium film layer.
15. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the hollow reflective
Tube material itself is to Raman scattering light reflection.
16. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the optical resonance
Chamber is externally provided with a concave mirror, and scattering light is reflected back through concave mirror inside hollow reflective pipe.
17. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the gas analysis
Instrument further includes gas sample room, and the optical resonator and hollow reflective pipe are located in gas sample room；Gas sample room is equipped with
Air inlet pipe and an air outlet pipe；Gas to be analyzed enters the gas sample room by air inlet pipe, is flowed through inside hollow reflective pipe, by going out
Tracheae flows out.
18. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the gaseous sample
Room is equipped at least one optical window；The scattering light being emitted from hollow reflective pipe is after the reflection of slant reflection mirror, from optical window
It projects.
19. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the laser and
A Faraday isolator is equipped between optical resonator.
20. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the laser and
A bandpass filter is equipped between optical resonator.
21. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the laser and
A short wave pass filter is equipped between optical resonator.
22. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the laser and
A laser beam enlarging bind device is equipped between optical resonator.
23. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the laser and
A laser beam attenuator is equipped between optical resonator.
24. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the scattering light is received
A long wave pass filter is equipped in acquisition means.
25. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the scattering light is received
A notch filtering light piece is equipped in acquisition means.
26. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the scattering light is received
Acquisition means connect spectrometer by fiber optic bundle.
27. the laser Raman spectroscopy gas analyzer as described in one of claim 1-12, which is characterized in that the scattering light is received
Packaging is set to two, is respectively used to receive backward Raman scattering and forward direction Raman scattering.
28. laser Raman spectroscopy gas analyzer as claimed in claim 26, which is characterized in that in the fiber optic bundle output end
Optical fiber is arranged in a row.
29. the laser Raman spectroscopy gas analyzer as described in one of claim 7-12, which is characterized in that the piezoelectric ceramics
Modulus (A/D) converter and digital-to-analogue (D/A) converter are equipped in control module.
30. the laser Raman spectroscopy gas analyzer as described in one of claim 7-12, which is characterized in that the piezoelectric ceramics
A voltage amplification module is equipped in control module.
31. the laser Raman spectroscopy gas analyzer as described in one of claim 7-12, which is characterized in that the piezoelectric ceramics
A central processing unit (CPU) is equipped in control module.
32. the laser Raman spectroscopy gas analyzer as described in one of claim 1-3, which is characterized in that the optical resonance
Chamber is made of three or four optical resonance resonant reflec-tors.
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| CN114923863B (en) * | 2022-05-26 | 2023-03-24 | 深圳市诺安智能股份有限公司 | Detection chamber with hollow tubule for detecting substance component |
| CN114994012B (en) * | 2022-05-26 | 2022-12-06 | 深圳市诺安智能股份有限公司 | Raman wave testing room with periodic groove tubule |
| CN115096779B (en) * | 2022-08-26 | 2023-06-30 | 苏州同人激光科技有限公司 | Vehicle-mounted gas quality detection system |
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Effective date of registration: 20161008 Address after: 778, room 304, building 8, 305 Asia Pacific Road, Nanhu District, Jiaxing, Zhejiang, Jiaxing, 314033 Applicant after: Jiaxing radium light Instrument Technology Co., Ltd. Address before: Yushan town of Kunshan City Road 215301 Suzhou city of Jiangsu province and fengyasong building 18 room 1306 Applicant before: Chen Liping Applicant before: Pei Shiyou |
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