WO2022120941A1 - 一种流体中卤族元素检测方法及检测系统 - Google Patents

一种流体中卤族元素检测方法及检测系统 Download PDF

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WO2022120941A1
WO2022120941A1 PCT/CN2020/138236 CN2020138236W WO2022120941A1 WO 2022120941 A1 WO2022120941 A1 WO 2022120941A1 CN 2020138236 W CN2020138236 W CN 2020138236W WO 2022120941 A1 WO2022120941 A1 WO 2022120941A1
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halogen
alkali metal
fluid
elements
laser
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PCT/CN2020/138236
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English (en)
French (fr)
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李祥友
汤志阳
刘可
周冉
张闻
刘坤
李青洲
朱晨薇
李阳
李殊涵
占凯平
曾晓雁
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华中科技大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/718—Laser microanalysis, i.e. with formation of sample plasma
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment

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  • the invention belongs to the field of laser-induced plasma emission spectrum detection, and more particularly, relates to a detection method and detection system for halogen elements in fluid.
  • the content of fluorine and chlorine elements in the aqueous solution is an important indicator for evaluating water quality. High levels of fluorine and chlorine elements will seriously endanger human health; too high content of halogenated hydrocarbons in industrial exhaust gas can cause damage to the ecological environment and personal safety. Serious hazards; therefore, rapid, accurate and real-time online detection of halogen elements in fluids (liquids/gases) is of great significance.
  • the detection of fluorine and chlorine in aqueous solution is mainly based on ion chromatography, and the detection of halogenated hydrocarbons in gas is mainly based on gas chromatography.
  • LIBS Laser-induced breakdown spectroscopy
  • the double-pulse LIBS irradiates the plasma with the laser of the second laser to realize the secondary excitation of the plasma, thereby improving the spectral intensity; spark discharge
  • the auxiliary LIBS injects new energy into the plasma through a high-voltage spark discharge device, thereby increasing the spectral intensity;
  • the microwave-assisted LIBS heats the plasma twice through a microwave device, thereby increasing the spectral intensity.
  • the present invention provides a detection method and detection system for halogen elements in fluids, which are used to solve the technical problems that the existing LIBS-based halogen element detection methods have complicated detection devices and high cost, which make practical application and promotion difficult.
  • a method for detecting halogen elements in a fluid comprising:
  • the fluid to be measured is ablated by laser, the medium is also ablated at the same time, and the plasma generated by laser ablation contains both alkali metal atoms and halogen atoms, and the alkali metal atoms and halogen atoms combine to form molecules;
  • the types and contents of halogen elements in the fluid to be tested are obtained.
  • the present invention provides a method for detecting halogen elements in a fluid based on laser-induced breakdown spectroscopy, wherein when the fluid containing halogen elements is laser ablated, the medium containing alkali metals is simultaneously ablated, The generated plasma contains halogen atoms to be detected and abundant alkali metal atoms.
  • the molecules formed by the combination of halogen elements and alkali metal elements will have a strong emission spectrum in the visible light region.
  • the molecular emission spectrum is used instead of the traditional detection method.
  • the atomic emission spectrum of halogen elements is used to analyze the information of halogen elements, which can effectively solve the problem that the atomic emission spectrum of halogen elements is weak in the visible light region, and can realize real-time online high-sensitivity detection of halogen elements.
  • this method does not increase the complexity and cost of the laser-induced breakdown spectroscopy device, retains the advantages of LIBS technology, such as fast detection speed, and is not limited by the sample type and environment, and can realize real-time online monitoring of halogen elements in fluids.
  • the present invention can also be improved as follows.
  • the process of forming molecules includes:
  • the solution is converted into an aerosol
  • the generated aerosol is led to the focal position of the laser, and the medium containing alkali metal elements is also located at the focal position of the laser;
  • the medium containing alkali metal elements is also ablated at the same time, and the plasma generated at this time contains alkali metal atoms and halogen atoms, and the alkali metal atoms and halogen atoms combine to form molecules;
  • the process of forming molecules includes:
  • the gas is directly led to the focal position of the laser, and the medium containing alkali metal elements is also located at the focal position of the laser;
  • the medium containing alkali metal elements is also ablated at the same time, and the plasma generated at this time contains alkali metal atoms and halogen atoms, which combine to form molecules.
  • the content of the alkali metal element satisfies:
  • the detected information of the emission spectrum of the molecule can be used to analyze the kind and content of the halogen element.
  • the mass fraction of alkali metal elements in the medium is relatively high
  • the mass fraction of alkali metal elements in the medium containing alkali metal elements used is very high
  • the plasma generated by ablation is rich in alkali metal atoms. It is beneficial to promote the combination of alkali metal atoms and halogen atoms in plasma, and obtain higher molecular spectrum intensity.
  • the detecting the spectral information emitted by the molecule is specifically detecting the visible light region spectral information emitted by the molecule.
  • the molecules formed by halogen elements and alkali metal elements generally have stronger emission spectrum intensity in the visible light region
  • the emission spectrum lines of the molecules formed by the combination of halogen group elements and alkali metal elements are generally located in the visible light region.
  • the detection efficiency of the detector in the visible light region is generally high, which can effectively improve the detection sensitivity of halogen elements in the fluid.
  • the medium is a solid matrix.
  • the further beneficial effects of the present invention are: compared with liquid and gas, the solid substrate is easier to detect and operate, and the operation is convenient.
  • the present invention also provides a halogen element detection system in a fluid, comprising:
  • Lasers for generating laser light
  • a medium containing alkali metal elements is used to be ablated at the focus position of the laser at the same time as the fluid to be tested containing halogen elements, and the generated plasma contains both the alkali metal atoms in the medium and the Measure the halogen atoms in the fluid, the alkali metal atoms and halogen atoms combine to form molecules;
  • a spectrum detection module for collecting light generated by the molecules in the plasma and converting it into a spectrum
  • the processor is configured to analyze the information of the spectrum to obtain the type and content of halogen elements in the fluid to be measured.
  • the present invention provides a detection system for halogen elements in a fluid based on laser-induced breakdown spectroscopy.
  • the medium containing alkali metals is simultaneously burned
  • the resulting plasma contains halogen atoms to be tested and abundant alkali metal atoms.
  • the molecules formed by the combination of halogen elements and alkali metal elements will have a strong emission spectrum in the visible light region.
  • the processor uses molecular emission spectrum instead of halogen element atomic emission spectrum used in traditional detection methods to analyze halogen element information, which can effectively solve the problem that the atomic emission spectrum of halogen elements is weak in the visible light region, and can realize halogen Real-time online high-sensitivity detection of group elements.
  • the system does not increase the complexity and cost of the laser-induced breakdown spectroscopy device, retains the advantages of LIBS technology, such as fast detection speed, and is not limited by sample types and environments, and can realize real-time online monitoring of halogen elements in fluids.
  • the content of the alkali metal element satisfies:
  • the detected information of the emission spectrum of the molecule can be used to analyze the kind and content of the halogen element.
  • the mass fraction of alkali metal elements in the medium is relatively high
  • the mass fraction of alkali metal elements in the medium containing alkali metal elements used is very high
  • the plasma generated by ablation is rich in alkali metal atoms. It is beneficial to promote the combination of alkali metal atoms and halogen atoms in plasma, and obtain higher molecular spectrum intensity.
  • the processor analyzes the information of the spectrum, specifically: analyze the spectrum information of the visible light region emitted by the molecule.
  • the molecules formed by halogen elements and alkali metal elements generally have stronger emission spectrum intensity in the visible light region
  • the emission spectrum lines of the molecules formed by the combination of halogen group elements and alkali metal elements are generally located in the visible light region.
  • the detection efficiency of the detector in the visible light region is generally high, which can effectively improve the detection sensitivity of halogen elements in the fluid.
  • the medium is a solid matrix.
  • the further beneficial effects of the present invention are: compared with liquid and gas, the solid substrate is easier to detect and operate, and the operation is convenient.
  • the spectral detection module includes: a light collection device, an optical fiber, a spectrometer, and a detector;
  • the light collection device collects the molecular optical signal generated by the transition of the molecule in the excited state to the ground state, and transmits it to the spectrometer through the optical fiber for light splitting, and then transmits it to the detector, and the detector pairs the obtained optical signal Photoelectric conversion, accumulation and amplification are performed to obtain spectra for analyzing halogen element information.
  • FIG. 1 is a flow chart of a method for detecting halogen elements in a fluid according to an embodiment of the present invention
  • FIG. 2 is a schematic diagram of a halogen element detection system in a fluid provided by an embodiment of the present invention
  • Fig. 3 is the CaF molecular emission spectrogram of the sodium fluoride solution that the embodiment of the present invention provides;
  • Fig. 4 is the CaCl molecular emission spectrogram of the sodium chloride solution provided in the embodiment of the present invention.
  • FIG. 5 is a schematic diagram of another halogen element detection system in a fluid provided by an embodiment of the present invention.
  • FIG. 6 is a CaF molecular emission spectrum diagram of trifluoromethane provided in an embodiment of the present invention.
  • 1 is a laser
  • 2 is a mirror
  • 3 is a focusing lens
  • 4 is a solid matrix containing alkali metal elements
  • 5 is a three-dimensional displacement platform
  • 6 is an optical collection path
  • 7 is an optical fiber
  • 8 is a spectrometer
  • 9 is a detector
  • 10 is Synchronous signal transmission line
  • 11 is a USB data transmission line
  • 12 is a computer
  • 13 is a gas atomizing device
  • 14 is a ventilation pipe
  • 15 is a gas collecting bottle.
  • a method for detecting halogen elements in fluid includes:
  • the fluid to be tested is ablated by laser, and the medium is also ablated at the same time.
  • the plasma generated by laser ablation contains both alkali metal atoms and halogen atoms, and the alkali metal atoms and halogen atoms combine to form molecules;
  • the type and content of halogen elements in the fluid to be tested can be obtained.
  • the medium containing alkali metal elements in this method can be solid, liquid or gas.
  • halogen element information based on spectral information
  • qualitative and quantitative analysis can be performed. That is, when the same solid matrix containing alkali metal is used, the emission spectrum band positions of molecules formed by the combination of different halogen elements and alkali metals in the fluid to be tested are different, and the types of halogen elements in the fluid can be obtained. Further, when the used solid substrates containing alkali metals are the same, the amount of alkali metal atoms generated by laser ablation of the substrates is the same. When laser ablation of the fluid to be measured with different concentrations of halogen, the amount of halogen atoms in the plasma is the same. are different, the number of molecules formed by combination is also different, and different emission spectrum intensities are obtained, thereby determining the content of halogen elements in the fluid to be tested.
  • a medium is selected, and the above-mentioned actual detection process is adopted for the fluid to be measured.
  • the same medium containing alkali metals is used, and different halogen elements in the fluid to be measured are used. Different from the emission spectrum band position of the molecule formed by the combination of alkali metal elements, the halogen element species in the fluid can be obtained, and qualitative analysis can be realized.
  • a medium is selected, and the above-mentioned actual detection process is adopted for the fluid to be measured.
  • the same medium containing alkali metals is used, and the alkali metal atoms generated by laser ablation of the medium are the same.
  • the amount is the same.
  • the amount of halogen atoms in the plasma is different, and the number of molecules formed by combination is also different, and different emission spectrum intensities are obtained, thereby determining the halogen in the fluid to be tested.
  • the content of elements can be quantitatively analyzed.
  • This embodiment provides a method for detecting halogen elements in a fluid based on laser-induced breakdown spectroscopy.
  • the fluid containing halogen elements is laser ablated
  • the medium containing alkali metals is simultaneously ablated, and the generated plasma contains
  • the halogen atoms to be detected and abundant alkali metal atoms, and the molecules formed by the combination of halogen elements and alkali metal elements will have a strong emission spectrum in the visible light region.
  • the molecular emission spectrum is used to replace the halogen atoms used in traditional detection methods.
  • the emission spectrum is used to analyze the information of halogen elements, which can effectively solve the problem that the atomic emission spectrum of halogen elements is weak in the visible light region, and can realize high-sensitivity detection of halogen elements.
  • this method does not increase the complexity and cost of the laser-induced breakdown spectroscopy device, retains the advantages of LIBS technology, such as fast detection speed, and is not limited by the sample type and environment, and can realize real-time online monitoring of halogen elements in fluids.
  • the above-mentioned process of forming molecules includes:
  • An aerosol device is used to convert the solution into an aerosol; the generated aerosol is led to the focal position of the laser, and the medium containing alkali metal elements is also located at the focal position of the laser; when the laser interacts with the aerosol, it contains The medium of alkali metal elements is also ablated at the same time, and the resulting plasma contains alkali metal atoms and halogen atoms, which combine to form molecules.
  • the medium containing alkali metal elements can be a solid matrix
  • an aerosolization system is used to convert the solution containing halogen elements into an aerosol, and then the generated aerosol is passed to the focal position of the laser, and contains alkali at the same time.
  • the surface of the solid substrate of the metal element is also located at the focal plane of the laser.
  • the laser interacts with the aerosol
  • the solid substrate containing the alkali metal element is also ablated, and the plasma generated at this time contains alkali metal atoms and the halogen to be measured.
  • Group atoms, the alkali metal atoms and halogen atoms in the plasma combine to form stable molecules.
  • the above-mentioned process of forming molecules includes:
  • the gas is directly led to the focal position of the laser, and the medium containing alkali metal elements is also located at the focal position of the laser; when the laser interacts with the gas, the medium containing alkali metal elements is also ablated at the same time, and the plasma generated at this time is also located at the focal position of the laser.
  • the medium containing alkali metal elements can be a solid matrix
  • the gas is directly passed to the focal position of the laser, and the surface of the solid substrate containing alkali metal elements is also located at the focal plane position of the laser.
  • the solid substrate containing alkali metal elements is also ablated at the same time, and the plasma generated at this time contains alkali metal atoms and halogen atoms to be measured, and the alkali metal atoms and halogen atoms in the plasma combine to form stable molecules
  • the content of alkali metal elements in the medium satisfies: the intensity of the emission spectrum of the detected molecules can be used to analyze the type and content of halogen elements.
  • the mass fraction of alkali metal elements in the medium is high, and the mass fraction of alkali metal elements in the medium containing alkali metal elements is high, and the plasma generated by ablation is rich in alkali metal atoms, which is conducive to promoting plasma
  • the combination of alkali metal atoms and halogen atoms in the plasma can obtain higher molecular spectrum intensity; on the other hand, the alkali metal atoms and halogen atoms contained in the plasma need to combine to form enough stable molecules to ensure the above detection.
  • the intensity of the spectrum emitted by the molecule can be used to analyze the type and content of halogen elements.
  • the "stable" means that the molecular dissociation energy formed by the combination of alkali metal atoms and halogen elements is relatively high, and can stably exist in the plasma, so as to generate a strong molecular emission spectrum.
  • the spectral information emitted by the detection molecule is specifically the spectral information of the visible light region emitted by the detection molecule.
  • Molecules formed by halogen elements and alkali metal elements generally have a strong emission spectrum in the visible light region, and the emission lines of molecules formed by the combination of halogen elements and alkali metal elements are generally located in the visible light region.
  • the detection efficiency is generally high, which can effectively improve the detection sensitivity of halogen elements in the fluid.
  • the acquisition efficiency of the ultraviolet spectrum is low, and because the intensity of the ultraviolet spectrum itself is very high, even if it is absorbed, it is sometimes enough to analyze the halogen elements.
  • the spectrum in the visible light region although there may be spectral line interference due to the acquisition environment, the collection efficiency in the ultraviolet spectral region is low after all, so the spectrum in the visible light region can meet the analysis of halogen elements.
  • the spectral information in the visible light region is preferably used, and the reliability is higher.
  • the above-mentioned medium is a solid matrix.
  • the alkali metal-containing medium used only needs to satisfy the high mass fraction of alkali metal elements, and the cost is low.
  • the solid substrate is easier to set up for detection and operation, and it is convenient to operate.
  • a detection system for halogen elements in fluid comprising: a laser, an optical path system, a medium containing alkali metal elements, a spectrum detection module and a computer.
  • Laser used to generate laser light
  • optical path system used to change the method of laser transmission and focus it
  • medium containing alkali metal elements used to be ablated at the focal position of the laser at the same time as the fluid to be tested containing halogen elements
  • the generated plasma contains both alkali metal atoms in the medium and halogen atoms in the fluid to be tested, and the alkali metal atoms and halogen atoms combine to form molecules
  • the spectrum detection module is used to collect the plasma The light generated by the molecule is converted into a spectrum
  • the computer is used to analyze the information of the spectrum to obtain the type and content of halogen elements in the fluid to be tested.
  • the fluid to be tested is a solution
  • the solution to be tested containing halogen elements is transformed into an aerosol through the aerosolization device 13 and transferred to the top of the surface of the solid substrate 4 containing alkali metal elements by the ventilation pipe 14 , while the fixed wavelength laser 1 emits laser light, the synchronization signal transmission line 10 transmits the signal to the detector 9 to prepare to receive the spectral signal.
  • the laser light emitted by the fixed wavelength laser 1 is first reflected by the mirror 2, and then focused by the focusing lens 3 on the base containing alkali.
  • the surface of the solid substrate 4 of metal elements when the solid substrate is ablated by the focused laser, the aerosol containing the halogen element to be measured is ablated at the same time, at this time, the generated plasma contains the halogen atoms to be measured and abundant alkali.
  • Metal atoms, halogen atoms and alkali metal atoms combine to form molecules, and the molecules in the excited state transition to the ground state to generate a molecular emission spectrum, which is then collected by the acquisition device 6 and transmitted to the spectrometer 8 through the optical fiber 7, and then transmitted to the detector 9 after being split by the spectrometer 8.
  • the detector 9 performs photoelectric conversion, accumulation and amplification on the obtained spectral signal, and transmits the data to the computer 12 through the USB data transmission line 11 .
  • the computer 12 processes the received spectral data to obtain the type and content of halogen elements in the solution to be measured.
  • the NaF aqueous solution containing 50 ppm of fluorine element and the NaCl aqueous solution containing 50 ppm of chlorine element were prepared respectively.
  • the laser selects Nd: YAG 1064 wavelength laser, and the spectrometer selects SCT320 type C-T structure spectrometer.
  • the emission line of CaF molecule at 529-535nm and the emission line of CaCl molecule at 593.4nm were selected as observation lines.
  • Calcite was chosen as the solid matrix, which is mainly composed of calcium carbonate.
  • the detection process is:
  • the focused laser ablates the aerosol solution and the solid matrix at the same time, and the generated plasma contains fluorine atoms and abundant calcium atoms, and the fluorine atoms and calcium atoms combine to form CaF molecules;
  • the CaF emission spectrum signal can be obtained.
  • the above-mentioned fluorine-containing aqueous solution can be replaced with a chlorine-containing aqueous solution to obtain the CaCl molecular emission spectrum signal.
  • halogen elements such as bromine, iodine, etc. can be combined with alkali metal elements calcium, barium, etc. to form Therefore, the method provided in Example 1 is expected to realize the high-sensitivity on-line detection of halogen elements in solution.
  • the gas to be measured in the gas collecting cylinder 15 is transferred from the vent pipe 14 to the surface of the solid base 4 containing alkali metal elements, and the laser 1 of the fixed wavelength emits laser light while The signal transmitted by the synchronization signal transmission line 10 to the detector 9 is ready to receive the spectral signal.
  • the laser light emitted by the fixed wavelength laser 1 is first reflected by the mirror 2, and then focused by the focusing mirror 3 on the surface of the solid substrate 4. When the focused laser ablates the solid When the substrate is used, the gas containing the halogen element to be measured is ablated at the same time.
  • the generated plasma contains the halogen atoms to be measured and abundant alkali metal atoms.
  • the halogen atoms combine with the alkali metal atoms to form molecules, and the excited state
  • the transition of the molecules to the ground state generates a molecular emission spectrum, which is then collected by the acquisition device 6 and transmitted to the spectrometer 8 through the optical fiber 7, and then transmitted to the detector 9 after being split by the spectrometer 8.
  • the detector 9 performs photoelectric conversion, accumulation and amplification on the obtained spectral signal.
  • the data is transmitted to the computer 12 by the USB data transmission line 11 .
  • the computer processes the received spectral data to obtain the type and content of halogen elements in the gas to be measured, thereby characterizing the type and content of the gas.
  • the method will be described by taking the detection of trifluoromethane (CHF 3 ) gas as an example.
  • the laser selected Nd YAG 1064 wavelength laser
  • Calcite is chosen as the solid matrix, which is mainly composed of calcium carbonate.
  • the detection process is:
  • the trifluoromethane gas is directly passed through the vent pipe to the vicinity of the surface of the calcite substrate;
  • the focused laser ablates trifluoromethane and the solid substrate at the same time, and the generated plasma contains fluorine atoms and abundant calcium atoms, and the fluorine atoms and calcium atoms combine to form CaF molecules;
  • the CaF emission spectrum signal can be obtained.
  • halogen elements such as chlorine, bromine, iodine, etc. can be combined with alkali metal elements calcium, barium, etc. Stable molecules are formed, therefore, the method provided in Example 1 is expected to realize high-sensitivity online detection of halogen elements in gas.
  • the content of the above-mentioned alkali metal elements satisfies that the intensity of the emission spectrum of the detected molecules can be used to analyze the type and content of halogen elements.
  • Relevant descriptions are the same as those in the first embodiment, and are not repeated here.
  • the computer when the computer analyzes the spectral information, it is specifically: analyzing the spectral information in the visible light region emitted by the molecule. Relevant descriptions are the same as those in the first embodiment, and are not repeated here.
  • the above-mentioned medium is a solid matrix. Relevant descriptions are the same as those in the first embodiment, and are not repeated here.

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Abstract

一种流体中卤族元素检测方法及检测系统，方法包括：将含有卤族元素的待测流体通向含有碱土金属元素的介质中；采用激光烧蚀待测流体，介质同时也被烧蚀，激光烧蚀产生的等离子体中同时含有碱土金属原子和卤族原子，碱土金属原子和卤族原子结合形成分子；通过检测分子所发射的光谱信息，得到待测流体中卤族元素的种类和含量。

Description

一种流体中卤族元素检测方法及检测系统 【技术领域】
本发明属于激光诱导等离子体发射光谱检测领域，更具体地，涉及一种流体中卤族元素检测方法及检测系统。
【背景技术】
水溶液中的氟和氯元素的含量是评价水质的重要指标，高含量的氟和氯元素将会严重危害人体的健康；工业排放废气中卤代烃的含量过高可对生态环境和人身安全造成严重危害；因此，快速、准确和实时在线的检测流体(液体/气体)卤素元素有着重要意义。目前，水溶液中氟和氯元素的检测主要以离子色谱法为主，气体中卤代烃的检测以气相色谱法为主，他们虽然能够准确的检测卤族元素的含量，但检测分析周期长，不能实时在线监测，时效性性差。激光诱导击穿光谱(Laser-induced breakdown spectroscopy,简称LIBS)是一种分析激光烧蚀样品产生等离子体的发射光谱技术，其通过发射光谱的信息实现对物质组成成分的种类和含量的测量。LIBS技术具有制样简单、检测速度快、实时和在线、不受样品种类和环境的限制等特点，在卤族元素检测领域，已经成为一种可行的工具。
然而，由于卤族元素特殊的能级结构(第一电离较大)，其较强的谱线处于真空紫外区域。但紫外光在空气中传播时存在容易被氧气吸收的问题，并且现有探测器在真空紫外的探测效率较低，LIBS技术在检测流体中卤素元素的灵敏度很难达到实际应用的检测标准。目前，为了改善激光诱导击穿光谱对卤族元素的检测灵敏度，一部分国内外学者通过将整个或部分LIBS检测装置置于真空或惰性环境中，来减弱真空紫外谱线被氧气吸收，从而提高光谱的强度，这种方法虽然能有效地提高LIBS技术对卤族元素的检测灵敏度，但由于其装置的复杂性和其检测条件的苛刻，使其仅仅适用 于实验室的分析，无法满足实际现场的实时在线分析。另一部分国内外学者通过选择卤族元素处于可见光区域较弱的谱线结合光谱增强方法，来提高LIBS技术对卤族元素的检测灵敏度，如双脉冲LIBS，火花放电辅助LIBS和微波辅助LIBS。这些技术都是通过对原有激光烧蚀样品产生的等离子体再作用，例如双脉冲LIBS通过第二束激光器的激光辐照等离子体，实现等离子体的二次激发，从而提高光谱强度；火花放电辅助LIBS通过高压火花放电装置往等离子体中注入新的能量，从而提高光谱强度；微波辅助LIBS通过微波装置对等离子体二次加热，从而提高光谱强度。由上可知，LIBS技术结合光谱增强方法虽然可以提高卤族元素原子谱线的光谱强度，但同时也增加了仪器装置的复杂性和成本，不利于实际应用的广泛推广。
【发明内容】
本发明提供一种流体中卤族元素检测方法及检测系统，用以解决现有基于LIBS的卤族元素检测方法存在检测装置复杂、成本高而导致难以实际应用推广的技术问题。
本发明解决上述技术问题的技术方案如下：一种流体中卤族元素检测方法，包括：
将含有卤族元素的待测流体通向含有碱金属元素的介质中；
采用激光烧蚀所述待测流体，所述介质同时也被烧蚀，激光烧蚀产生的等离子体中同时含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子；
通过检测所述分子所发射的光谱信息，得到所述待测流体中卤族元素的种类和含量。
本发明的有益效果是：本发明提供一种基于激光诱导击穿光谱的流体中卤族元素的检测方法，其激光烧蚀含卤族元素的流体时，含碱金属的介质同时被烧蚀，产生的等离子体中含有待测卤族原子和丰富的碱金属原子，卤族元素与碱金属元素结合形成的分子在可见光区域会有很强的发射光谱 强度，利用分子发射光谱代替传统检测方法所采用的卤族元素原子发射光谱，来分析卤族元素信息，可以有效解决卤族元素的原子发射光谱在可见光区域较弱的问题，可以实现卤族元素的实时在线高灵敏度检测。此外，该方法没有增加激光诱导击穿光谱装置的复杂性和成本，保留了LIBS技术检测速度快、不受样品种类和环境的限制等优势，可以实现对流体中卤族元素的实时在线监测。
上述技术方案的基础上，本发明还可以做如下改进。
进一步，当所述待测流体为溶液时，所述形成分子的过程包括：
采用气雾化装置，将该溶液转变成气溶胶；
将产生的气溶胶通向激光的焦点位置，同时含有碱金属元素的介质也位于激光的焦点位置；
在激光与气溶胶相互作用时，含有碱金属元素的介质同时也被烧蚀，此时产生的等离子中含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子；
当所述待测流体为气体时，所述形成分子的过程包括：
将该气体直接通向激光的焦点位置，同时含有碱金属元素的介质也位于激光的焦点位置；
在激光与气体相互作用时，含有碱金属元素的介质同时也被烧蚀，此时产生的等离子中含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子。
进一步，所述碱金属元素的含量满足：
检测的所述分子所发射光谱的信息能够用于分析所述卤族元素的种类和含量。
本发明的进一步有益效果是：介质中碱金属元素质量分数较高，使用的含有碱金属元素的介质中碱金属的质量分数很高，烧蚀产生的等离子体中含有丰富的碱金属原子，有利于促进等离子体中碱金属原子与卤族原子 的结合，获得较高的分子光谱强度。
进一步，所述检测所述分子所发射的光谱信息具体为检测所述分子所发射的可见光区域光谱信息。
本发明的进一步有益效果是：卤族元素与碱金属元素形成的分子，处于可见光区域的发射光谱强度一般较强，且卤族元素与碱金属元素结合形成的分子的发射谱线一般位于可见光区域，目前探测器在可见光区域的探测效率一般较高，可以有效提高流体中卤族元素的检测灵敏度。
进一步，所述介质为固体基体。
本发明的进一步有益效果是：固体基体相比较液体、气体，易于检测操作的设置，方便操作。
本发明还提供一种流体中卤族元素检测系统，包括：
激光器，用于产生激光；
光路系统，用于改变所述激光的传输方向并对激光进行聚焦；
含有碱金属元素的介质，用于与含有卤族元素的待测流体同时在所述激光的焦点位置被烧蚀，所产生的等离子体中同时含有所述介质中的碱金属原子和所述待测流体中的卤族原子，该碱金属原子和卤族原子结合形成分子；
光谱探测模块，用于采集所述等离子体中所述分子产生的光并转换为光谱；
处理器，用于分析所述光谱的信息，得到所述待测流体中卤族元素的种类和含量。
本发明的有益效果是：本发明提供一种基于激光诱导击穿光谱的流体中卤族元素的检测系统，激光器产生的激光烧蚀含卤族元素的流体时，含碱金属的介质同时被烧蚀，产生的等离子体中含有待测卤族原子和丰富的碱金属原子，卤族元素与碱金属元素结合形成的分子在可见光区域会有很强的发射光谱强度，光谱探测模块探测分子发射的光谱，处理器利用分子 发射光谱代替传统检测方法所采用的卤族元素原子发射光谱，来分析卤族元素信息，可以有效解决卤族元素的原子发射光谱在可见光区域较弱的问题，可以实现卤族元素的实时在线高灵敏度检测。此外，该系统没有增加激光诱导击穿光谱装置的复杂性和成本，保留了LIBS技术检测速度快、不受样品种类和环境的限制等优势，可以实现对流体中卤族元素的实时在线监测。
进一步，所述碱金属元素的含量满足：
检测的所述分子所发射光谱的信息能够用于分析所述卤族元素的种类和含量。
本发明的进一步有益效果是：介质中碱金属元素质量分数较高，使用的含有碱金属元素的介质中碱金属的质量分数很高，烧蚀产生的等离子体中含有丰富的碱金属原子，有利于促进等离子体中碱金属原子与卤族原子的结合，获得较高的分子光谱强度。
进一步，所述处理器分析所述光谱的信息时具体为：分析所述分子所发射的可见光区域光谱信息。
本发明的进一步有益效果是：卤族元素与碱金属元素形成的分子，处于可见光区域的发射光谱强度一般较强，且卤族元素与碱金属元素结合形成的分子的发射谱线一般位于可见光区域，目前探测器在可见光区域的探测效率一般较高，可以有效提高流体中卤族元素的检测灵敏度。
进一步，所述介质为固体基体。
本发明的进一步有益效果是：固体基体相比较液体、气体，易于检测操作的设置，方便操作。
进一步，所述光谱探测模块包括：光采集装置，光纤，光谱仪，以及探测器；
所述光采集装置收集激发态的所述分子向基态跃迁所产生的分子光信号，并通过所述光纤传输至所述光谱仪以分光，之后传输至探测器，所述 探测器对获得的光信号进行光电转换、积累和放大处理，得到用于分析卤族元素信息的光谱。
【附图说明】
图1为本发明实施例提供的一种流体中卤族元素检测方法流程框图；
图2为本发明实施例提供的一种流体中卤族元素检测系统示意图；
图3为本发明实施例提供的氟化钠溶液的CaF分子发射光谱图；
图4为本发明实施例提供的氯化钠溶液的CaCl分子发射光谱图；
图5为本发明实施例提供的另一种流体中卤族元素检测系统示意图；
图6为本发明实施例提供的三氟甲烷的CaF分子发射光谱图。
在所有附图中，相同的附图标记用来表示相同的元件或者结构，其中：
1为激光器，2为反射镜，3为聚焦透镜，4为含碱金属元素的固体基体，5为三维位移平台，6为采集光路，7为光纤，8为光谱仪，9为探测器，10为同步信号传输线，11为USB数据传输线，12为计算机，13气雾化装置，14为通气管，15为集气瓶。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例一
一种流体中卤族元素检测方法，如图1所示，包括：
将含有卤族元素的待测流体通向含有碱金属元素的介质中；
采用激光烧蚀待测流体，介质同时也被烧蚀，激光烧蚀产生的等离子体中同时含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子；
通过检测分子所发射的光谱信息，得到待测流体中卤族元素的种类和含量。
该方法中含有碱金属元素的介质可以是固体、液体或气体。
另外，在基于光谱信息进行卤族元素信息分析时，可以进行定性和定量分析。也就是，在使用的含有碱金属的固体基体相同时，待测流体中不同的卤素元素与碱金属结合形成的分子的发射光谱谱带位置不同，可以得到流体中的卤素元素种类。进一步地，在使用的含有碱金属的固体基体相同时，激光烧蚀基体产生的碱金属原子的量是相同的，激光烧蚀不同浓度卤素的待测流体时，等离子体中卤素的原子的量是不同的，结合形成的分子数目也不同，得到不同发射光谱强度，从而确定待测流体中卤族元素的含量。
具体的，对于定性分析，选用一个介质，对待测流体采取上述实际检测过程，其中针对该待测流体中不同的卤族元素，使用的含有碱金属的介质相同，待测流体中不同的卤素元素与碱金属元素结合形成的分子的发射光谱谱带位置不同，可以得到流体中的卤素元素种类，实现定性分析。
对于定量分析，选用一个介质，对待测流体采取上述实际检测过程，其中针对该待测流体中不同浓度的卤族元素，使用的含有碱金属的介质相同，激光烧蚀介质产生的碱金属原子的量是相同的，激光烧蚀不同浓度卤素的待测流体时，等离子体中卤素原子的量是不同的，结合形成的分子数目也不同，得到不同发射光谱强度，从而确定待测流体中卤族元素的含量，实现定量分析。
本实施例提供一种基于激光诱导击穿光谱的流体中卤族元素的检测方法，其激光烧蚀含卤族元素的流体时，含碱金属的介质同时被烧蚀，产生的等离子体中含有待测卤族原子和丰富的碱金属原子，卤族元素与碱金属元素结合形成的分子在可见光区域会有很强的发射光谱强度，利用分子发射光谱代替传统检测方法所采用的卤族元素原子发射光谱，来分析卤族元 素信息，可以有效解决卤族元素的原子发射光谱在可见光区域较弱的问题，可以实现卤族元素的高灵敏度检测。此外，该方法没有增加激光诱导击穿光谱装置的复杂性和成本，保留了LIBS技术检测速度快、不受样品种类和环境的限制等优势，可以实现对流体中卤族元素的实时在线监测。
优选的，当待测流体为溶液时，上述形成分子的过程包括：
采用气雾化装置，将该溶液转变成气溶胶；将产生的气溶胶通向激光的焦点位置，同时含有碱金属元素的介质也位于激光的焦点位置；在激光与气溶胶相互作用时，含有碱金属元素的介质同时也被烧蚀，此时产生的等离子中含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子。
例如，当含有碱金属元素的介质可以是固体基体时，首先采用气雾化系统，将含有卤族元素的溶液转变成气溶胶，然后将产生的气溶胶通至激光的焦点位置，同时含有碱金属元素的固体基板表面也位于激光的焦平面位置，在激光与气溶胶相互作用时，含有碱金属元素的固体基板同时也被烧蚀，此时产生的等离子中含有碱金属原子和待测卤族原子，等离子中碱金属原子和卤族原子结合形成稳定的分子。
当所述待测流体为气体时，上述形成分子的过程包括：
将该气体直接通向激光的焦点位置，同时含有碱金属元素的介质也位于激光的焦点位置；在激光与气体相互作用时，含有碱金属元素的介质同时也被烧蚀，此时产生的等离子中含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子。
例如，当含有碱金属元素的介质可以是固体基体时，将气体直接通至激光的焦点位置，同时含有碱金属元素的固体基板表面也位于激光的焦平面位置，在激光与气体相互作用时，含有碱金属元素的固体基板同时也被烧蚀，此时产生的等离子中含有碱金属原子和待测卤族原子，等离子中碱金属原子和卤族原子结合形成稳定的分子
优选的，介质中碱金属元素的含量满足：检测的分子所发射光谱的强度能够用于分析卤族元素的种类和含量。
一方面，也就是介质中碱金属元素质量分数较高，使用的含有碱金属元素的介质中碱金属的质量分数很高，烧蚀产生的等离子体中含有丰富的碱金属原子，有利于促进等离子体中碱金属原子与卤族原子的结合，获得较高的分子光谱强度；另一方面，等离子体中含有的碱金属原子和卤族原子需要结合形成足够的稳定的分子，以保证上述检测的分子所发射光谱的强度能够用于分析卤族元素的种类和含量。其中所述“稳定”是指碱金属原子与卤族元素结合形成的分子离解能较高，能稳定的存在于等离子体中，以便产生较强的分子发射光谱。
优选的，上述检测分子所发射的光谱信息具体为检测分子所发射的可见光区域光谱信息。
卤族元素与碱金属元素形成的分子，处于可见光区域的发射光谱强度一般较强，且卤族元素与碱金属元素结合形成的分子的发射谱线一般位于可见光区域，目前探测器在可见光区域的探测效率一般较高，可以有效提高流体中卤族元素的检测灵敏度。
在采集过程中由于被环境吸收等因素，紫外光谱的采集效率低，而由于紫外光谱的强度本身非常高，因此即便被吸收，有时也是够用于分析卤族元素的。对于可见光区域光谱，虽然因采集环境可能会有谱线干扰，但毕竟紫外光谱区域采集效率低，因此可见光区域光谱是能够满足卤族元素的分析。这里优选采用可见光区域光谱信息，可靠性高一些。
优选的，上述介质为固体基体。
如前所述，使用的含有碱金属的介质仅仅需满足碱金属元素的质量分数较高即可，成本较低。
另外，固体基体相比较液体、气体，易于检测操作的设置，方便操作。
实施例二
一种流体中卤族元素检测系统，包括：激光器，光路系统，含有碱金属元素的介质，光谱探测模块以及处计算机。其中，
激光器，用于产生激光；光路系统，用于改变激光传输的方法并对其进行聚焦；含有碱金属元素的介质，用于与含有卤族元素的待测流体同时在激光的焦点位置被烧蚀，所产生的等离子体中同时含有介质中的碱金属原子和所述待测流体中的卤族因为原子，该碱金属原子和卤族原子结合形成分子；光谱探测模块，用于采集等离子体中所述分子产生的光并转换为光谱；计算机，用于分析光谱的信息，得到待测流体中卤族元素的种类和含量。
当待测流体为溶液时，如图2所示，将含卤族元素的待测溶液通过气雾化装置13变成气溶胶由通气管14传输至含碱金属元素的固体基体4的表面上方，固定波长的激光器1发出激光的同时由同步信号传输线10传递信号给探测器9准备接收光谱信号，固定波长的激光器1发出的激光首先经反射镜2反射，然后由聚焦透镜3聚焦于含碱金属元素的固体基体4的表面，当聚焦激光烧蚀固体基体时，含待测卤族元素的气溶胶同时被烧蚀，此时，产生的等离子体中含有待测的卤族原子和丰富碱金属原子，卤族原子与碱金属原子结合形成分子，激发态的分子向基态跃迁产生分子发射光谱，然后由采集装置6收集通过光纤7传输至光谱仪8，经由光谱仪8分光后传输至探测器9，探测器9对获得的光谱信号进行光电转换、积累和放大，由USB数据传输线11将数据传输至计算机12。最后，计算机12对接受的光谱数据进行处理，得到待测溶液中卤族元素的种类和含量。
例如，以检测水溶液中的氟和氯元素为例，对该方法进行详细的说明。
分别配置含氟元素为50ppm的NaF水溶液和含氯元素为50ppm的NaCl水溶液。
激光器选择Nd：YAG 1064波长的激光器，光谱仪选择SCT320型的 C-T结构型光谱仪。选取CaF分子发射谱线529-535nm和CaCl分子发射谱线593.4nm为观察谱线。
选择方解石为固体基体，其主要由碳酸钙组成。
检测流程为：
将含氟溶液放入气雾化装置中，将其雾化成气溶胶状态并通至方解石基体表面上方附近；
打开激光器输出激光，聚焦后的激光同时烧蚀气溶胶溶液和固体基体，产生的等离子中含有氟原子和丰富的钙原子，氟原子和钙原子结合形成CaF分子；
观察等离子体的发射光谱，可以得到CaF发射光谱信号。
将上述的含氟元素水溶液换成含氯元素的水溶液可以得到CaCl分子发射光谱信号。
为了证明基体中需含丰富碱金属元素的必要性，选择载玻片为一种对比基体，如图3所示，在仅烧蚀方解石和烧蚀载玻片上的气溶胶时，观察不到CaF分子发射光谱，只有烧蚀在方解石基体上方的氟化钠气溶胶溶液时可以观察到明显的氟化钙分子发射光谱信号。图4也表明只有烧蚀在方解石基体上方的氯化钠气溶胶溶液时可以观察到明显的氯化钙分子发射光谱信号。
综上所述，使用实施例提供的方法和系统可以显著的检测到溶液中氟和氯元素，在等离子体中，像溴、碘等卤族元素都可与碱金属元素钙、钡等结合形成稳定的分子，因此，实施例一提供的方法有望实现溶液中卤族元素的高灵敏度在线检测。
当待测流体为气体时，如图5所示，将集气瓶15中待测气体由通气管14传输至含碱金属元素的固体基体4的表面上方，固定波长的激光器1发出激光的同时由同步信号传输线10传递信号给探测器9准备接收光谱信号，固定波长的激光器1发出的激光首先经反射镜2反射，然后由聚焦镜3聚 焦于固体基体4的表面，当聚焦激光烧蚀固体基体时，含待测卤族元素的气体同时被烧蚀，此时，产生的等离子体中含有待测的卤族原子和丰富碱金属原子，卤族原子与碱金属原子结合形成分子，激发态的分子向基态跃迁产生分子发射光谱，然后由采集装置6收集通过光纤7传输至光谱仪8，经由光谱仪8分光后传输至探测器9，探测器9对获得的光谱信号进行光电转换、积累和放大，由USB数据传输线11将数据传输至计算机12。最后，计算机对接受的光谱数据进行处理，得到待测气体中卤族元素的种类和含量，从而表征气体的种类和含量。
例如，以检测三氟甲烷(CHF 3)气体为例子，对该方法进行说明。
用三氟甲烷气体标准物质。
激光器选择Nd：YAG 1064波长的激光器，光谱仪选择ME5000型的中阶梯型结构光谱仪。选取CaF为观察谱线。
选择方解石为固体基体，其主要有碳酸钙组成。
检测流程为：
将三氟甲烷气体直接通过通气管通至方解石基体表面上方附近；
打开激光器输出激光，聚焦后的激光同时烧蚀三氟甲烷和固体基体，产生的等离子中含有氟原子和丰富的钙原子，氟原子和钙原子结合形成CaF分子；
观察等离子体的发射光谱，可以得到CaF发射光谱信号。
如图6所示，激光单独烧蚀方解石时，检测不到CaF的分子光谱，当将三氟甲烷通至方解石基体表面的上方时，用激光烧蚀可以观察明显CaF分子发射光谱。
综上所述，使用本实施例提供的方法和系统可以显著地检测到气体中氟元素，在等离子体中，像氯、溴、碘等卤族元素都可与碱金属元素钙、钡等结合形成稳定的分子，因此，实施例一提供的方法有望实现气体中卤族元素的高灵敏度在线检测。
优选的，上述碱金属元素的含量满足：检测的分子所发射光谱的强度能够用于分析卤族元素的种类和含量。相关说明同实施例一，在此不再赘述。
优选的，计算机分析光谱的信息时具体为：分析分子所发射的可见光区域光谱信息。相关说明同实施例一，在此不再赘述。
优选的，上述介质为固体基体。相关说明同实施例一，在此不再赘述。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种流体中卤族元素检测方法，其特征在于，包括：
    将含有卤族元素的待测流体通向含有碱金属元素的介质中；
    采用激光烧蚀所述待测流体，所述介质同时也被烧蚀，激光烧蚀产生的等离子体中同时含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子；
    通过检测所述分子所发射的光谱信息，得到所述待测流体中卤族元素的种类和含量。
  2. 根据权利要求1所述的一种流体中卤族元素检测方法，其特征在于，当所述待测流体为溶液时，所述形成分子的过程包括：
    采用气雾化装置，将该溶液转变成气溶胶；
    将产生的气溶胶通向激光的焦点位置，同时含有碱金属元素的介质也位于激光的焦点位置；
    在激光与气溶胶相互作用时，含有碱金属元素的介质同时也被烧蚀，此时产生的等离子中含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子；
    当所述待测流体为气体时，所述形成分子的过程包括：
    将该气体直接通向激光的焦点位置，同时含有碱金属元素的介质也位于激光的焦点位置；
    在激光与气体相互作用时，含有碱金属元素的介质同时也被烧蚀，此时产生的等离子中含有碱金属原子和卤族原子，该碱金属原子和卤族原子结合形成分子。
  3. 根据权利要求1所述的一种流体中卤族元素检测方法，其特征在于，所述碱金属元素的含量满足：
    检测的所述分子所发射光谱的信息能够用于分析所述卤族元素的种类 和含量。
  4. 根据权利要求1至3任一项所述的一种流体中卤族元素检测方法，其特征在于，所述检测所述分子所发射的光谱信息具体为检测所述分子所发射的可见光区域光谱信息。
  5. 根据权利要求1至3任一项所述的一种流体中卤族元素检测方法，其特征在于，所述介质为固体基体。
  6. 一种流体中卤族元素检测系统，其特征在于，包括：
    激光器，用于产生激光；
    光路系统，用于改变所述激光的传输方向并对激光进行聚焦；
    含有碱金属元素的介质，用于与含有卤族元素的待测流体同时在所述激光的焦点位置被烧蚀，所产生的等离子体中同时含有所述介质中的碱金属原子和所述待测流体中的卤族原子，该碱金属原子和卤族原子结合形成分子；
    光谱探测模块，用于采集所述等离子体中所述分子产生的光并转换为光谱；
    处理器，用于分析所述光谱的信息，得到所述待测流体中卤族元素的种类和含量。
  7. 根据权利要求6所述的一种流体中卤族元素检测系统，其特征在于，所述碱金属元素的含量满足：
    检测的所述分子所发射光谱的信息能够用于分析所述卤族元素的种类和含量。
  8. 根据权利要求6所述的一种流体中卤族元素检测系统，其特征在于，所述处理器分析所述光谱的信息时具体为：分析所述分子所发射的可见光区域光谱信息。
  9. 根据权利要求6所述的一种流体中卤族元素检测系统，其特征在于，所述介质为固体基体。
  10. 根据权利要求6至9任一项所述的一种流体中卤族元素检测系统，其特征在于，所述光谱探测模块包括：光采集装置，光纤，光谱仪，以及探测器；
    所述光采集装置收集激发态的所述分子其向基态跃迁所产生的分子光信号，并通过所述光纤传输至所述光谱仪以分光，之后传输至探测器，所述探测器对获得的光信号进行光电转换、积累和放大处理，得到用于分析卤族元素信息的光谱。
PCT/CN2020/138236 2020-12-11 2020-12-22 一种流体中卤族元素检测方法及检测系统 WO2022120941A1 (zh)

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