技术领域technical field
本发明涉及一种气体检测方法，特别涉及一种基于交叉闭合光路的激光拉曼气体检测方法。The invention relates to a gas detection method, in particular to a laser Raman gas detection method based on a cross-closed optical path.
背景技术Background technique
石油，天然气等能源的开采存在着大量的混合气体，如何有效地将油气混合气体中不同气体检测分离出来是油气开采中的关键。传统的检测方法，如气相色谱技术，存在着不能连续检测，且维护费用大的问题，而红外光谱技术，有限的检测范围也使其只能应用与相应环境下。因此，寻求一种有效的气体检测方法，该方法应能连续有效地分辨出多种气体，并有着较高的精度，对石油化工的发展有着极大的意义。拉曼光谱技术的应用使之成为可能。There are a lot of mixed gases in the exploitation of oil, natural gas and other energy sources. How to effectively detect and separate different gases in the oil-gas mixed gas is the key to oil and gas exploitation. Traditional detection methods, such as gas chromatography technology, have the problems of not being able to detect continuously and having high maintenance costs, while infrared spectroscopy technology, with its limited detection range, can only be used in corresponding environments. Therefore, it is of great significance to seek an effective gas detection method, which should be able to continuously and effectively distinguish a variety of gases, and have high precision, for the development of petrochemical industry. The application of Raman spectroscopy technology makes this possible.
先前的设计中，例如美国AIR公司生产的多路拉曼气体检测仪器，以及中国实用新型专利，专利名称：一种录井用拉曼光谱检测系统，专利号：ZL201120284529.2。这些设计都对气体检测提出一些较好的措施，但是设计中采用的是单路谐振腔，利用激光在两面镜之间来回振荡。有时不仅激光强度难以得到保障，杂散光的影响也难以消除。In the previous design, for example, the multi-channel Raman gas detection instrument produced by the American AIR company, and the Chinese utility model patent, the patent name: a Raman spectrum detection system for mud logging, the patent number: ZL201120284529.2. These designs all put forward some better measures for gas detection, but the design uses a single-channel resonant cavity, which uses laser light to oscillate back and forth between two mirrors. Sometimes not only the laser intensity is difficult to be guaranteed, but also the influence of stray light is difficult to eliminate.
发明内容Contents of the invention
本发明是针对现在拉曼气体检测仪器存在的问题，提出了一种基于交叉闭合光路的激光拉曼气体检测系统，采用全新的交叉闭合振荡光路设计，改善单路光路带来的回返光影响，实现在线多种气体的测量。The present invention aims at the problems existing in current Raman gas detection instruments, and proposes a laser Raman gas detection system based on a cross-closed optical path, which adopts a brand-new cross-closed oscillation optical path design to improve the impact of return light brought by a single optical path, Realize online measurement of multiple gases.
本发明的技术方案为：一种基于交叉闭合光路的激光拉曼气体检测系统，包括反应室、反应室上下的进出气管，反应室上面用于采集反应室内信号的光谱仪模块，两个两端带布鲁斯特窗的高压氦氖玻璃管，三棱镜，4个反射镜，两高压氦氖玻璃管对称斜插入反应室同侧，第一反射镜、第一高压氦氖管、三棱镜和第二反射镜依次放置在同一轴线上，第四反射镜、第二高压氦氖管和第三反射镜对应与第一反射镜、第一高压氦氖管和第二反射镜以反应室中心水平线对称放置；The technical solution of the present invention is: a laser Raman gas detection system based on a cross-closed optical path, including a reaction chamber, air inlet and outlet pipes up and down the reaction chamber, a spectrometer module above the reaction chamber for collecting signals in the reaction chamber, two ends with The high-pressure helium-neon glass tube of the Brewster window, the triangular prism, and 4 reflectors, two high-pressure helium-neon glass tubes are inserted symmetrically and obliquely into the same side of the reaction chamber, the first reflector, the first high-pressure helium-neon tube, the triangular prism and the second reflector in sequence Placed on the same axis, the fourth reflector, the second high-pressure helium-neon tube and the third reflector are placed symmetrically with the first reflector, the first high-pressure helium-neon tube and the second reflector on the horizontal line in the center of the reaction chamber;
从第一高压氦氖管射出的氦氖激光，通过第一反光镜折射到达第四反射镜，再折射通过第二高压氦氖管，到达第三反射镜，再折射到达第二反射镜，再经过三棱镜和第一高压氦氖管到达第一反射镜，形成一个闭合交叉环式光路；从第二高压氦氖管射出的氦氖激光，依次经过第三反射镜折射后到达第二反射镜，再经过三棱镜和第一高压氦氖管，到达第一反射镜，再折射到达第四反射镜，被折射后经过第二高压氦氖管到达第三反射镜，形成另一闭合交叉环式光路；The helium-neon laser emitted from the first high-pressure helium-neon tube is refracted by the first reflector to the fourth reflector, then refracted through the second high-pressure helium-neon tube, reaches the third reflector, refracts to the second reflector, and then After passing through the prism and the first high-pressure helium-neon tube, it reaches the first reflector, forming a closed cross-ring optical path; the helium-neon laser emitted from the second high-voltage helium-neon tube is refracted by the third reflector in turn, and then reaches the second reflector, After passing through the triangular prism and the first high-pressure helium-neon tube, it reaches the first reflector, and then refracts to the fourth reflector. After being refracted, it passes through the second high-voltage helium-neon tube and reaches the third reflector, forming another closed cross-ring optical path;
多路气体由反应室上的进气口进入反应室，与激光反应产生拉曼信号，混合光通过光谱仪模块收集，光谱仪模块处理信号送计算机分析生成拉曼频谱图。The multi-channel gas enters the reaction chamber through the air inlet on the reaction chamber, and reacts with the laser to generate a Raman signal. The mixed light is collected by the spectrometer module, and the spectrometer module processes the signal and sends it to the computer for analysis to generate a Raman spectrum.
所述高压氦氖管两端的布鲁斯特窗滤除了S偏振，使光线转换为线偏振光。The Brewster windows at both ends of the high-pressure helium-neon tube filter out the S polarization and convert the light into linearly polarized light.
所述三棱镜放置在反应室外，按频率对光产生色散，分开各个频率的振荡光，具有选模作用。The triangular prism is placed outside the reaction chamber, produces dispersion to light according to frequency, separates oscillating light of each frequency, and has the function of mode selection.
所述光谱仪模块依次包括滤光片、单色仪以及传感器，接收的混合光中拉曼信号99%被滤光片透过后，单色仪收集光谱能量后送传感器。The spectrometer module sequentially includes a filter, a monochromator and a sensor. After 99% of the Raman signal in the received mixed light is passed through the filter, the monochromator collects spectral energy and sends it to the sensor.
本发明的有益效果在于：本发明基于交叉闭合光路的激光拉曼气体检测系统，结合有源腔增强技术和拉曼气体检测技术，采用有源腔，避免了无源腔的结构松散，采用交叉环式光路，降低了单路光路带来的回返光影响。系统具有拉曼光谱技术和高精度检测的特点，能同时在线测量多种气体，并进行实时在线分析。整个系统紧凑，可靠性高，检测效果优良，有较好的操作性。The beneficial effect of the present invention is that: the laser Raman gas detection system based on the cross closed optical path of the present invention combines the active cavity enhancement technology and the Raman gas detection technology, adopts the active cavity, avoids the loose structure of the passive cavity, and adopts the cross The ring optical path reduces the impact of return light caused by a single optical path. The system has the characteristics of Raman spectroscopy technology and high-precision detection, and can simultaneously measure multiple gases online and perform real-time online analysis. The whole system is compact, with high reliability, excellent detection effect and good operability.
附图说明Description of drawings
图1为本发明基于交叉闭合光路的激光拉曼气体检测系统示意图。FIG. 1 is a schematic diagram of a laser Raman gas detection system based on a cross-closed optical path according to the present invention.
具体实施方式detailed description
如图1所示基于交叉闭合光路的激光拉曼气体检测系统示意图，反应室601上下有进出气管101、102；反应室601上面还有光谱仪模块201采集反应室601内信号；301，302为两端带有布鲁斯特窗的高压氦氖玻璃管，两高压氦氖玻璃管对称斜插入反应室，且位于同一侧；401为三棱镜；501、502、503、504为反射镜。激光由高压氦氖管中产生，反射镜501，高压氦氖管301，三棱镜401和反射镜502依次放置在同一轴线上，反射镜504，高压氦氖管302和反射镜503对应与反射镜501，高压氦氖管301和反射镜502以反应室601中心水平线对称放置。反射镜501与反射镜502相对于高压氦氖管302平行放置，反射镜503与反射镜504相对于高压氦氖管301平行放置。As shown in Figure 1, a schematic diagram of a laser Raman gas detection system based on a crossed closed optical path, the reaction chamber 601 has inlet and outlet air pipes 101, 102 above and below; the reaction chamber 601 also has a spectrometer module 201 to collect signals in the reaction chamber 601; 301, 302 are two A high-pressure He-Ne glass tube with a Brewster window at the end, two high-pressure He-Ne glass tubes are inserted into the reaction chamber obliquely and symmetrically, and are located on the same side; 401 is a prism; 501, 502, 503, and 504 are reflecting mirrors. The laser light is generated by a high-pressure helium-neon tube, the reflector 501, the high-pressure helium-neon tube 301, the prism 401 and the reflector 502 are sequentially placed on the same axis, the reflector 504, the high-pressure helium-neon tube 302 and the reflector 503 correspond to the reflector 501 , the high-pressure HeNe tube 301 and the reflector 502 are placed symmetrically with respect to the central horizontal line of the reaction chamber 601 . The reflector 501 and the reflector 502 are placed parallel to the high-pressure HeNe tube 302 , and the reflector 503 and the reflector 504 are placed parallel to the high-pressure HeNe tube 301 .
具体实施过程：The specific implementation process:
波长为632.8nm的氦氖激光从高压氦氖管发出，一路从高压氦氖管301射出，通过反光镜501折转60度到达反射镜504，再折转60度经过高压氦氖管302，到达反射镜503，折转60度到达反射镜502，再经过三棱镜401，高压氦氖管301到达反射镜501，形成闭合交叉环式光路。另一路从高压氦氖管302射出，依次经过反射镜503，折转后到达反射镜502，再经过三棱镜401，高压氦氖管301，到达反射镜501，再折转到达反射镜504，折转后经过高压氦氖管302到达反射镜503，形成另一闭合交叉环式光路。多路气体从进气口进入反应室，与激光进行反应产生拉曼信号，再通过光谱仪模块中的滤光片和单色仪，再经过雪崩光电二极管，最后由计算机系统分析检测生成拉曼频谱图。本系统成功进行了包含氧气和氮气的混合气体的在线检测，本系统具有结构紧凑，交叉环式光路，稳定性好，可靠性上佳，便于操作；能同时测量多种气体，灵敏度高，适应性强，便于维护等特点。The helium-neon laser with a wavelength of 632.8nm is emitted from the high-pressure helium-neon tube, shoots all the way from the high-pressure helium-neon tube 301, turns 60 degrees through the reflector 501 to reach the reflector 504, and then turns 60 degrees through the high-pressure helium-neon tube 302 to reach The reflector 503 is bent by 60 degrees to reach the reflector 502, then passes through the prism 401, and the high-pressure He-Ne tube 301 reaches the reflector 501, forming a closed cross-ring optical path. The other way is emitted from the high-pressure helium-neon tube 302, passes through the reflector 503 in turn, reaches the reflector 502 after turning, then passes through the prism 401, the high-pressure helium-neon tube 301, reaches the reflector 501, and then turns to reach the reflector 504. Afterwards, it passes through the high-pressure helium-neon tube 302 and reaches the reflector 503 to form another closed cross-ring optical path. The multi-channel gas enters the reaction chamber from the inlet, reacts with the laser to generate Raman signals, then passes through the filter and monochromator in the spectrometer module, and then passes through the avalanche photodiode, and finally is analyzed and detected by the computer system to generate a Raman spectrum picture. This system has successfully carried out on-line detection of mixed gases containing oxygen and nitrogen. This system has a compact structure, a cross-ring optical path, good stability, good reliability, and easy operation; it can measure multiple gases at the same time, with high sensitivity and adaptability. Strong, easy to maintain and so on.
避免了无源腔增强技术的结构松散；避免了单路结构所带来的回返光干扰。具有拉曼光谱技术和高精度检测的特点，能实现在线实时测量和多路气体同时检测。整个系统操作便捷，易于维护，稳定性上佳。Avoid the loose structure of the passive cavity enhancement technology; avoid the return light interference caused by the single-channel structure. With the characteristics of Raman spectroscopy technology and high-precision detection, it can realize online real-time measurement and simultaneous detection of multiple gases. The whole system is easy to operate, easy to maintain, and has good stability.
所述平面反射镜，该反射镜的反射率高达95%，与光路成60度。As for the plane reflector, the reflectivity of the reflector is as high as 95%, and it forms 60 degrees with the light path.
所述光谱仪模块由单色仪，传感器和滤光片组成，滤光片对于拉曼光具有99%的透过率，而其它光线仅有5%的透过率。单色仪较好收集光谱能量，而传感器及后续检测器件则对光谱进行分析与检测。The spectrometer module is composed of a monochromator, a sensor and an optical filter. The optical filter has a transmittance of 99% for Raman light, while the transmittance of other light is only 5%. The monochromator is better at collecting spectral energy, while the sensor and subsequent detection devices analyze and detect the spectrum.
所述布鲁斯特窗滤除了S偏振，使光线转换为线偏振光。The Brewster window filters out S polarization, converting the light to linearly polarized light.
所述三棱镜能按频率对光进行色散，将各个频率的振荡光分离开来，具有选模作用。The triangular prism can disperse the light according to the frequency, separate the oscillating light of each frequency, and has the effect of mode selection.
所述两个高压氦氖管，提供了较强的初始激发光强。The two high-pressure helium-neon tubes provide strong initial excitation light intensity.
所述交叉环式光路存在交叉聚焦点，提高振荡激发光的激发强度。There is a cross focus point in the cross ring optical path, which improves the excitation intensity of the oscillation excitation light.
所述光线在交叉环式光路循环反射振荡，光线的振荡次数显著增加。The light is cyclically reflected and oscillated in the cross-ring optical path, and the number of oscillations of the light is significantly increased.
所述光线在交叉光路循环反射振荡，有利于杂散光经过反射镜时因散射角的变化溢出，减少非激发光的振荡。Said light cyclically reflects and oscillates in the intersecting optical path, which is beneficial to the overflow of stray light due to the change of scattering angle when passing through the reflector, and reduces the oscillation of non-exciting light.
所述三棱镜在反应室外，有利于杂散光的散射溢出，提高光线质量。The triangular prism is outside the reaction chamber, which is conducive to the scattering and overflow of stray light and improves the quality of light.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610022876.5ACN105548139B (en) | 2016-01-14 | 2016-01-14 | A kind of LR laser raman gas detecting system that light path is closed based on intersection |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610022876.5ACN105548139B (en) | 2016-01-14 | 2016-01-14 | A kind of LR laser raman gas detecting system that light path is closed based on intersection |
| Publication Number | Publication Date |
|---|---|
| CN105548139Atrue CN105548139A (en) | 2016-05-04 |
| CN105548139B CN105548139B (en) | 2018-06-29 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610022876.5AActiveCN105548139B (en) | 2016-01-14 | 2016-01-14 | A kind of LR laser raman gas detecting system that light path is closed based on intersection |
| Country | Link |
|---|---|
| CN (1) | CN105548139B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106198490A (en)* | 2016-08-17 | 2016-12-07 | 中国原子能科学研究院 | A kind of spatial deviation Raman spectroscopic detection system |
| CN108535191A (en)* | 2018-06-15 | 2018-09-14 | 上海理工大学 | LR laser raman gas-detecting device based on diamond shape hysteroscope |
| CN112748102A (en)* | 2021-01-04 | 2021-05-04 | 远正(江苏)水务科技有限公司 | Active cavity traveling wave field enhanced gas Raman detection device |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3704951A (en)* | 1969-06-11 | 1972-12-05 | Cary Instruments | S light cell for increasing the intensity level of raman light emission from a sample |
| US4648714A (en)* | 1985-09-11 | 1987-03-10 | University Of Utah | Molecular gas analysis by Raman scattering in intracavity laser configuration |
| CN102305784A (en)* | 2011-05-13 | 2012-01-04 | 北京师范大学 | Rapid laser Raman spectrum hydrocarbon detection method for drilling fluid |
| CN203606290U (en)* | 2013-12-12 | 2014-05-21 | 无锡萤光海光电科技有限公司 | Raman system |
| CN103837520A (en)* | 2014-03-03 | 2014-06-04 | 上海理工大学 | Optic travelling wave cavity enhanced laser raman gas concentration detection device |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3704951A (en)* | 1969-06-11 | 1972-12-05 | Cary Instruments | S light cell for increasing the intensity level of raman light emission from a sample |
| US4648714A (en)* | 1985-09-11 | 1987-03-10 | University Of Utah | Molecular gas analysis by Raman scattering in intracavity laser configuration |
| CN102305784A (en)* | 2011-05-13 | 2012-01-04 | 北京师范大学 | Rapid laser Raman spectrum hydrocarbon detection method for drilling fluid |
| CN203606290U (en)* | 2013-12-12 | 2014-05-21 | 无锡萤光海光电科技有限公司 | Raman system |
| CN103837520A (en)* | 2014-03-03 | 2014-06-04 | 上海理工大学 | Optic travelling wave cavity enhanced laser raman gas concentration detection device |
| Title |
|---|
| 胡佳惠 等: "布里渊散射的分布式光纤温度传感器的研究进展", 《激光杂志》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106198490A (en)* | 2016-08-17 | 2016-12-07 | 中国原子能科学研究院 | A kind of spatial deviation Raman spectroscopic detection system |
| CN108535191A (en)* | 2018-06-15 | 2018-09-14 | 上海理工大学 | LR laser raman gas-detecting device based on diamond shape hysteroscope |
| CN112748102A (en)* | 2021-01-04 | 2021-05-04 | 远正(江苏)水务科技有限公司 | Active cavity traveling wave field enhanced gas Raman detection device |
| Publication number | Publication date |
|---|---|
| CN105548139B (en) | 2018-06-29 |
| Publication | Publication Date | Title |
|---|---|---|
| CN103076310B (en) | Spectrum detection system for material component analysis and detection method thereof | |
| CN105572099B (en) | LR laser raman gas-detecting device based on homocentric hysteroscope | |
| CN110044824B (en) | A dual-spectrum gas detection device and method based on quartz tuning fork | |
| CN101644673A (en) | Infrared cavity ring-down spectroscopy trace gas detection method based on quantum cascade laser | |
| CN103115894B (en) | Stable isotopic abundance ratio real-time online monitoring device and method | |
| CN114047136B (en) | A high-sensitivity combined light source photoacoustic spectroscopy gas detection system and method | |
| CN104364635A (en) | Collisional broadening compensation using real or near-real time validation in spectroscopic analyzers | |
| CN104614317B (en) | A kind of quartz tuning fork strengthened optoacoustic spectroscopy detection means of two-tube side-by-side | |
| CN101819140A (en) | Continuous monitoring device and method of gaseous elemental mercury concentration | |
| CN101256140A (en) | Portable device and measurement method for simultaneously monitoring sulfur dioxide and nitric oxide gas concentrations | |
| Zhang et al. | Optical technology for detecting the decomposition products of SF6: a review | |
| CN105466854A (en) | Active air-chamber structure and photoacoustic spectrometry gas sensing system | |
| CN105548139B (en) | A kind of LR laser raman gas detecting system that light path is closed based on intersection | |
| Zhao et al. | All-optical photoacoustic detection of SF6 decomposition component SO2 based on fiber-coupled UV-LED | |
| CN104568910A (en) | Slit beam-splitting Raman spectrum gas analysis system applied to logging site | |
| CN108535191B (en) | Laser Raman gas detection device based on diamond cavity mirror | |
| CN102590097B (en) | Mercury vapor continuous monitoring method based on diode laser | |
| CN203224448U (en) | Spectral detection system for analyzing material composition | |
| CN116380838A (en) | Greenhouse gas measurement system and method based on multipath infrared laser absorption spectrum | |
| CN108398421A (en) | A kind of enhanced laser induced breakdown spectrograph of distinguishable carbon isotope | |
| CN204389393U (en) | A kind of integrated gas detection system | |
| CN108535192A (en) | LR laser raman gas-detecting device based on Multi-path proportional detection | |
| CN108572159A (en) | A laser reflective detection device for the content of CO2 and H2O in multiple thermal fluid components | |
| CN108444972A (en) | A kind of laser gas Raman spectroscopic detection system based on capillary enhancing | |
| CN109270004B (en) | Atmospheric analysis and detection system and detection method based on DOAS and LIBS technology |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | Effective date of registration:20191125 Address after:Room 1410-1411, North building, No. 1699, Zuchongzhi South Road, Yushan Town, Kunshan City, Suzhou City, Jiangsu Province Patentee after:Kunshan Shangli Optoelectronic Information Application Technology Research Institute Co., Ltd Address before:200093 Shanghai military road, Yangpu District, No. 516 Patentee before:University of Shanghai for Science and Technology | |
| TR01 | Transfer of patent right | ||
| CP02 | Change in the address of a patent holder | Address after:Room 1410-1411, North building, No. 1699, Zuchongzhi South Road, Yushan Town, Kunshan City, Suzhou City, Jiangsu Province Patentee after:Kunshan Shangli Optoelectronic Information Application Technology Research Institute Co., Ltd Address before:Room 1410-1411, North building, No. 1699, Zuchongzhi South Road, Yushan Town, Kunming City, Jiangsu Province 215000 Patentee before:Kunshan Shangli Optoelectronic Information Application Technology Research Institute Co., Ltd | |
| CP02 | Change in the address of a patent holder |