CN104777145A - Raman spectrum system aiming at industrial gas multi-component analysis - Google Patents
Raman spectrum system aiming at industrial gas multi-component analysis Download PDFInfo
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- CN104777145A CN104777145A CN201510117714.5A CN201510117714A CN104777145A CN 104777145 A CN104777145 A CN 104777145A CN 201510117714 A CN201510117714 A CN 201510117714A CN 104777145 A CN104777145 A CN 104777145A
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Abstract
The invention relates to the field of gas spectrum analysis instruments, and relates to a Raman spectrum system aiming at industrial gas multi-component analysis. The system comprises a gas cavity (9) and an optical path part. One side of the gas cavity (9) is provided with a window plate (10). The optical path part comprises a lens (3), a dichroscope (2), a light filter (4), a convergent lens (5), and a spectrometer (6); wherein the lens (3), dichroscope (2), light filter (4), convergent lens (5), and spectrometer (6) are in the same optical path, and the lens (3) is opposite to the window plate (10). The lens (3) is used to focus the excited light beams, and the focus is in the gas cavity (9). The inner length of the gas cavity (9) is not shorter than 4 cm. The gas inlet pipeline (14) and gas outlet pipeline (15) of the gas cavity (9) are respectively provided with a device for controlling the pressure so as to maintain a constant pressure in the gas cavity (9). The provided system can effectively enhance the Raman scattering signals so as to fulfill the requirements of industrial gas multi-component analysis.
Description
Art
The present invention relates to gas spectrometer device field, particularly a kind of Raman spectrum system for industrial gasses multicomponent analysis.
Background technology
Along with the fast development of China's economic, industrial gasses are as one of foundation of national economy industry key element, and the critical role in national economy and effect highlight day by day.In the present invention, industrial gasses mainly comprise the whole organic and inorganic gas except inert gas, relate to the process gas product in the fields such as petrochemical complex, oil-gas exploration, Gas Energy Source, iron and steel, cement, food, papermaking, environmental monitoring, energy-saving and emission-reduction or final gaseous product, it accurately fast detects will directly decide operational efficiency and the economic benefit of relevant industries, and provide foundation for the optimal control in later stage.But, due to the complicacy of Multi-Component Gas Analyzing, its detection technique is stagnated for many years, particularly embody a concentrated reflection of the field such as oil-gas exploration, Gas Energy Source, detect while relating to organic and inorganic gas, be difficult to adopt same technology it to be carried out to the detection of space-time uniformity, often need to adopt knockdown gas detection technology, cause the analysis efficiency of related industry low, and have a strong impact on further developing of related industry.
Traditional Multi-Component Gas Analyzing method has: vapor-phase chromatography, infrared spectroscopy, ultraviolet difference photometry, analysis of thermal conductivity method and the electrochemical methods being representative with various electrochemical gas sensor, and these methods are mostly difficult to realize detecting while organic and inorganic gas simultaneously.Wherein vapor-phase chromatography needs to utilize chromatographic column to carry out separation and concentration to gas, time-consuming, effort, costly, and consumptive material needed for instrument is numerous, it is complicated to safeguard, causes its detection efficiency deviation, is difficult to meet the demand that industrial gasses detect in real time.Infrared spectroscopy and ultraviolet difference photometry cannot detect non-polar gas composition, and analysis of thermal conductivity method is non-specific physical detection technology, its sensor application scope is narrower, pot life many factors, and the polycomponent that cannot meet industrial gasses particularly complicated gas detects simultaneously.Although electrochemical gas sensor volume is little, price is low, but it is not high to the resolution of gas, often be subject to environmental gas interference in using and occur wrong report, situation about failing to report, and sensor easily poisoning, serviceable life is low, therefore cannot meet the accuracy requirement that industrial gasses detect.And the Raman spectrum detection technique used in the present invention, then efficiently solve the problem existing for said method.
What early stage Raman spectrum detecting instrument adopted is filter sheet structure, the spectral information that this structure obtains is only some the isolated spectral slice in Raman spectrogram, if publication number is the detection method proposed in the patent of CN104198461A, the method only can analyze 4-16 kind fixed gas composition simultaneously, has certain limitation in commercial Application.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of spectroscopic analysis system that can carry out full spectral analysis to polycomponent industrial gasses is provided.The present invention is by using gas Raman spectrum detection technique, and the high flux polycomponent realizing industrial gasses detects simultaneously; By carrying out supercharging to gas cell to improve molecular density, by reducing laser beam spot sizes to increase the depth of field, thus realize higher detection sensitivity by simple mode; Meanwhile, in order to improve the stability of system, internal system is provided with complete temperature, control pressurer system, makes its performance meet the actual demand that in each field, industrial gasses detect.Technical scheme of the present invention is as follows:
For a Raman spectrum system for industrial gasses multicomponent analysis, comprising: air chamber (9) and light path part, offer window (10) in the side of air chamber (9); Described light path part comprises the lens (3) be arranged in successively in same light path, dichroic mirror (2), light filter (4), convergent lens (5) and spectrometer (6), described lens (3) are just to window (10), wherein
Laser instrument (1), for generation of excitation beam;
Dichroic mirror (2), for reflects laser topknot, allows Raman scattering light beam to pass through;
Lens (3), for focusing on excitation beam, its focus is positioned at air chamber (9), and the aperture angle scope of lens (3) is at 30 °-80 °; Excitation beam diameter excitation beam diameter, at 0.5mm-5mm, is less than the diameter of lens (3), and the Raman scattering luminous energy before and after focus in field depth is coupled into lens (3);
Light filter (4), for filtering excitation beam;
Convergent lens (5), for converging to spectrometer (6) by Raman diffused light;
Spectrometer (6), for analyzing the Raman diffused light after overconvergence;
Air chamber (9) inner length is not shorter than 4cm;
The admission line (14) and outlet pipe (15) of air chamber (9) are respectively arranged with the device of controlled pressure, for carrying out Isobarically Control to air chamber (9), make cavity pressure stablize supercharging under a certain pressure, the span of described certain pressure is being greater than 1 atmospheric pressure and is being less than between 100 atmospheric pressure.
Preferably, the device of described controlled pressure is reduction valve (12,13).Cavity pressure is stabilized in 10 atmospheric pressure.Excitation beam diameter is 1mm, and the aperture angle scope of lens (3) is at 50 °.Described system also comprises thermostatically-controlled equipment (8), for keeping the temperature stabilization of light path part, to ensure the steady operation of optics.Described system also comprises gas circuit heating apparatus (16), for heating to gas piping, under being all in gaseous state to make whole components of industrial gasses to be measured.Air chamber air admission hole (11) and window (10) have certain angle, be advisable to 70 degree with 20 degree, window (10) can be purged during to ensure that gas to be measured flows into air chamber (9), effectively reduce the dead volume in air chamber (9) simultaneously.
The Raman spectrum system for industrial gasses multicomponent analysis that the present invention proposes is on the basis of Raman spectrum detection technique in early days, introduce Raman ensemble spectrum detection technique, this technology can carry out holistic approach to Raman spectrogram, obtain spectral information more comprehensively, solve the problem that early stage Raman spectrum detecting instrument cannot detect all interested organic and inorganic gas simultaneously.Meanwhile, the present invention proposes the concept of depth of field control at Raman spectrum detection field, have employed in gordian techniquies such as gas circuit purging, gas boosting, system constant temperature, is controlled by the depth of field, effectively promotes raman spectral signal collecting efficiency; Adopt inclination purging technology, while maintenance window is clean, also reduces gas dead volume; Adopt the method for gas circuit supercharging, effectively improve the detection sensitivity of system; The pretreatment mode that use system constant temperature, gas circuit are heated, improves the stability of Raman spectrum system.
Accompanying drawing explanation
Fig. 1 is the Raman spectrum system for industrial gasses multicomponent analysis provided by the invention.
In figure, 1 is laser instrument, and 2 is dichroic mirror, 3 is lens, and 4 is optical filter, and 5 is convergent lens, 6 is spectrometer, and 7 is CCD, and 8 is thermostatically-controlled equipment, 9 is air chamber, and 10 is window, and 11 is air chamber air admission hole, 1213 is reduction valve, 14 is admission line, and 15 is outlet pipe, and 16 is gas circuit heating apparatus.
Fig. 2 is the Raman spectrum of oxygen, nitrogen, methane.
Fig. 3 is the catalogue of the industrial gasses that can detect with Raman spectrum system analysis of the present invention.
Embodiment
Below in conjunction with accompanying drawing, be described in detail as follows.Described herein mainly for the implementation method of the Raman spectrum system of industrial gasses multicomponent analysis.
Fig. 1 shows the structural representation of the Raman spectrum system for industrial gasses multicomponent analysis provided by the invention, and details are as follows.
It is 400nm-1550nm that laser instrument 1 produces wavelength coverage, and power bracket is 50mW-2W, and live width scope is the excitation beam of 0.01nm-0.6nm.
The laser center wavelength that the present embodiment adopts is 450nm, power is the excitation beam of 0.1nm at about 100mW and live width.
The Raman scattering light beam that dichroic mirror 2 allows wavelength longer passes through, and the excitation beam that reflection wavelength is shorter, but only rely on dichroic mirror 2 cannot remove excitation beam completely, therefore need optical filter 4 filtering excitation beam further.
Lens 3 pairs of excitation beams focus on, and its focus is positioned at air chamber 9, and excitation beam diameter, at 0.5mm-5mm, is less than the diameter of lens 3; The aperture angle scope of lens 3 is at 30 °-80 °.The present embodiment adopts diameter to be the light beam of 1mm, and the aperture angle scope of lens 3 is at 50 °.
The present invention controls owing to introducing the depth of field, and excitation beam adopts light pencil incident, during focusing the convergent angle of light beam and the angle of divergence all smaller, therefore before and after focus, certain space scope inner laser intensity is all very high, thus increases the spatial dimension of the gas that is excited.And when collecting, the Raman diffused light before and after focus in field depth can be coupled into lens 3, therefore greatly improve the collection efficiency of system to Raman scattering signal, and then effectively improve the detection sensitivity of system.
Wherein, the excitation beam of optical filter 4 filtering 450nm.
Raman diffused light is converged to the slit place of spectrometer 6 by convergent lens 5.
Spectrometer 6 should be corresponding with the centre wavelength of laser instrument 1 with a point optical range of CCD7, and resolution should be less than 10cm-1, and its F value will match with convergent lens 5, and spectrometer F value used herein is 2.
Thermostatically-controlled equipment 8 by the temperature stabilization of the light path part of Raman spectrum system at about 15 DEG C, to ensure the steady operation of optics.
Air chamber 9 inner length should be not less than 4cm, and the length of the present embodiment is 5cm, to reduce cavity rear end spurious signal to the interference of gas Raman scattered signal.
Window 10 is circular quartz window, thickness 3mm, to ensure that air chamber can not be broken under pressurized state.
Air chamber air admission hole 11 should have certain angle with window 10, is advisable with 30 °, can purge window 10, effectively reduce the dead volume in air chamber 9 simultaneously during to ensure that gas to be measured flows into air chamber 9.
Reduction valve 12,13 for carrying out Isobarically Control to air chamber 9, and to ensure the stability of gas circuit, two reduction valve match simultaneously, and realize cavity supercharging, boost range is between 1 ~ 100 atmospheric pressure.Usually can control at 10 atm higher.In this way, effectively can increase gas molecule quantity in cavity, thus Raman scattering signal intensity is improved 1 ~ 2 order of magnitude.
Industrial gasses enter system by admission line 14, and the gas after analysis discharges system by outlet pipe 15.
Gas circuit heating apparatus 16 is by gas piping, the temperature comprising air chamber 9 and the corresponding parts such as admission line 14, outlet pipe 15 is warmed to more than 50 DEG C, under being all in gaseous state to make whole components of industrial gasses to be measured, thus ensure that accuracy and the stability of analytic system.
Fig. 2 illustrates that system records the Raman spectrum of oxygen, nitrogen, methane.
Main Basis Raman scattering effect of the present invention is to the accurate reflection of gas molecule energy level variations, because the feature of the change of gas molecule energy level and gas molecule structure is closely connected and possesses uniqueness, so Raman spectrum can identify other gas molecule structure except inert gas, accurately distinguish each industrial gasses.Meanwhile, organically combine chemometrics method, the Accurate Determining of industrial gasses component content information can be realized.By the direct measurement of industrial gasses, accurately can estimate value or the harmfulness of gas, as fuel value, greenhouse effect, toxicity etc., being the core composition of the industry on-line analyses such as gas industry, oil-gas exploration, petrochemical complex, iron and steel, cement, food, papermaking, environmental monitoring, energy-saving and emission-reduction, is also the key that related industries realizes optimized control.Therefore, the method has broad application prospects in low-carbon (LC) society and Ecological Civilization Construction.
Claims (7)
1. for a Raman spectrum system for industrial gasses multicomponent analysis, comprising: air chamber (9) and light path part, offer window (10) in the side of air chamber (9); Described light path part comprises the lens (3) be arranged in successively in same light path, dichroic mirror (2), light filter (4), convergent lens (5) and spectrometer (6), described lens (3) are just to window (10), wherein
Laser instrument (1), for generation of excitation beam;
Dichroic mirror (2), for reflects laser topknot, allows Raman scattering light beam to pass through;
Lens (3), for focusing on excitation beam, its focus is positioned at air chamber (9), and the aperture angle scope of lens (3) is at 30 °-80 °; Excitation beam diameter excitation beam diameter, at 0.5mm-5mm, is less than the diameter of lens (3), and the Raman scattering luminous energy before and after focus in field depth is coupled into lens (3);
Light filter (4), for filtering excitation beam;
Convergent lens (5), for converging to spectrometer (6) by Raman diffused light;
Spectrometer (6), for analyzing the Raman diffused light after overconvergence;
Air chamber (9) inner length is not shorter than 4cm;
The admission line (14) and outlet pipe (15) of air chamber (9) are respectively arranged with the device of controlled pressure, for carrying out Isobarically Control to air chamber (9), make cavity pressure stablize supercharging under a certain pressure, the span of described certain pressure is being greater than 1 atmospheric pressure and is being less than between 100 atmospheric pressure.
2. Raman spectrum system according to claim 1, is characterized in that, the device of described controlled pressure is reduction valve (12,13).
3. Raman spectrum system according to claim 1, is characterized in that, cavity pressure is stabilized in 10 atmospheric pressure.
4. Raman spectrum system according to claim 1, is characterized in that, excitation beam diameter is 1mm, and the aperture angle scope of lens (3) is at 50 °.
5. Raman spectrum system according to claim 1, is characterized in that, described system also comprises thermostatically-controlled equipment (8), for keeping the temperature stabilization of light path part, to ensure the steady operation of optics.
6. Raman spectrum system according to claim 1, is characterized in that, described system also comprises gas circuit heating apparatus (16), for heating to gas piping, under being all in gaseous state to make whole components of industrial gasses to be measured.
7. Raman spectrum system according to claim 1, it is characterized in that, air chamber air admission hole (11) and window (10) have certain angle, be advisable to 70 degree with 20 degree, window (10) can be purged during to ensure that gas to be measured flows into air chamber (9), effectively reduce the dead volume in air chamber (9) simultaneously.
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| CN201510117714.5A CN104777145A (en) | 2015-05-21 | 2015-05-21 | Raman spectrum system aiming at industrial gas multi-component analysis |
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| CN108802009A (en) * | 2018-08-24 | 2018-11-13 | 哈尔滨工业大学（威海） | A method of detecting heavy metal using plasma atomic emission spectrometer |
| CN108872080A (en) * | 2018-08-24 | 2018-11-23 | 哈尔滨工业大学（威海） | A kind of preceding light path system of plasma atomic emission spectrometer |
| CN110673330A (en) * | 2019-09-02 | 2020-01-10 | 南京理工大学 | Imaging system depth of field expanding device and method based on scattering |
| CN111879727A (en) * | 2020-06-22 | 2020-11-03 | 中国科学院合肥物质科学研究院 | Receiving and transmitting same-side light path structure, device and application of multiband detection for gas monitoring |
| IT202000027308A1 (en) * | 2020-11-16 | 2021-02-16 | Sense Square S R L | Raman Air Quality Monitoring (SMR) System |
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Application publication date: 20150715 |