CN112595704A - Method and system for detecting halogen elements in fluid - Google Patents
Method and system for detecting halogen elements in fluid Download PDFInfo
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Abstract
The invention belongs to the field of laser-induced plasma emission spectrum detection, and particularly discloses a method and a system for detecting halogen elements in fluid, wherein the method comprises the following steps: leading the fluid to be tested containing the halogen element into a medium containing an alkali metal element; the fluid to be detected is ablated by laser, the medium is ablated at the same time, plasma generated by laser ablation contains alkali metal atoms and halogen atoms at the same time, and the alkali metal atoms and the halogen atoms are combined to form molecules; and obtaining the type and content of the halogen element in the fluid to be detected by detecting the spectral information emitted by the molecules. The invention adopts laser to ablate fluid containing halogen element and medium containing alkali metal element at the same time, obtain very strong molecule emission spectrum, analyze the information of halogen element through the molecule emission spectrum, solve the problem that the atomic emission spectrum of the halogen element is weaker in the visible light area effectively, realize the real-time online high-sensitivity detection of the halogen element, the apparatus is simple, the detection speed is fast, unrestricted by environment.
Description
Technical Field
The invention belongs to the field of laser-induced plasma emission spectrum detection, and particularly relates to a method and a system for detecting halogen elements in fluid.
Background
The content of fluorine and chlorine elements in the aqueous solution is an important index for evaluating water quality, and the high content of fluorine and chlorine elements can seriously harm the health of human bodies; the high content of the halogenated hydrocarbon in the industrial exhaust gas can cause serious harm to the ecological environment and the personal safety; therefore, the rapid, accurate and real-time online detection of the halogen element in the fluid (liquid/gas) is of great significance. At present, the detection of fluorine and chlorine elements in an aqueous solution is mainly carried out by ion chromatography, the detection of halogenated hydrocarbon in gas is mainly carried out by gas chromatography, and although the detection and analysis period is long and the content of halogen elements can be accurately detected, the detection and analysis period cannot be monitored on line in real time, and the timeliness is poor. Laser-induced breakdown spectroscopy (LIBS) is an emission spectroscopy technique for analyzing plasma generated by Laser ablation of a sample, and the kind and content of a substance component are measured through the information of the emission spectroscopy. The LIBS technology has the characteristics of simple sample preparation, high detection speed, real-time and on-line performance, no limitation of sample types and environments and the like, and becomes a feasible tool in the field of halogen element detection.
However, due to the special energy level structure of halogen elements (the first ionization is larger), the stronger spectral line is in the vacuum ultraviolet region. However, ultraviolet light is easy to be absorbed by oxygen when being transmitted in air, the detection efficiency of the existing detector in vacuum ultraviolet is low, and the sensitivity of the LIBS technology in detecting halogen elements in fluid hardly reaches the detection standard of practical application. At present, in order to improve the detection sensitivity of laser-induced breakdown spectroscopy to halogen elements, a part of domestic and foreign scholars reduce the absorption of vacuum ultraviolet spectral lines by oxygen by placing the whole or part of LIBS detection device in a vacuum or inert environment, so as to improve the intensity of the spectroscopy. The other part of domestic and foreign scholars can improve the sensitivity of LIBS technology for detecting halogen elements by selecting a spectral line with weak halogen element in a visible light region and combining a spectrum enhancement method, such as double-pulse LIBS, spark discharge auxiliary LIBS and microwave auxiliary LIBS. The technologies realize secondary excitation of plasma by re-acting the plasma generated by the original laser ablation sample, for example, the double-pulse LIBS irradiates the plasma through the laser of a second beam laser, thereby improving the spectral intensity; the spark discharge auxiliary LIBS injects new energy into the plasma through the high-voltage spark discharge device, so that the spectral intensity is improved; the microwave-assisted LIBS heats the plasma a second time by a microwave device, thereby increasing the spectral intensity. From the above, although the LIBS technology combined with the spectrum enhancement method can improve the spectrum intensity of the atomic spectral line of halogen elements, the complexity and cost of the instrument are increased, which is not favorable for the wide popularization of practical application.
Disclosure of Invention
The invention provides a method and a system for detecting halogen elements in fluid, which are used for solving the technical problem that the existing method for detecting halogen elements based on LIBS is difficult to be practically applied and popularized due to the fact that a detection device is complex and the cost is high.
The technical scheme for solving the technical problems is as follows: a method for detecting halogen in a fluid, comprising:
leading the fluid to be tested containing the halogen element into a medium containing an alkali metal element;
the fluid to be detected is ablated by laser, the medium is ablated at the same time, plasma generated by laser ablation contains alkali metal atoms and halogen atoms at the same time, and the alkali metal atoms and the halogen atoms are combined to form molecules;
and obtaining the type and the content of the halogen element in the fluid to be detected by detecting the spectral information emitted by the molecules.
The invention has the beneficial effects that: the invention provides a method for detecting halogen elements in fluid based on laser-induced breakdown spectroscopy, wherein when the fluid containing the halogen elements is ablated by laser, a medium containing alkali metals is ablated at the same time, the generated plasma contains halogen atoms to be detected and abundant alkali metal atoms, molecules formed by combining the halogen elements and the alkali metal elements have strong emission spectrum intensity in a visible light region, the molecular emission spectrum is used for replacing the halogen element atom emission spectrum adopted by the traditional detection method to analyze halogen element information, the problem that the atomic emission spectrum of the halogen elements is weak in the visible light region can be effectively solved, and the real-time online high-sensitivity detection of the halogen elements can be realized. In addition, the method does not increase the complexity and the cost of a laser-induced breakdown spectroscopy device, retains the advantages of high detection speed of the LIBS technology, no limitation of sample types and environments and the like, and can realize real-time online monitoring on the halogen elements in the fluid.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, when the fluid to be measured is a solution, the process of forming molecules includes:
converting the solution into an aerosol using an aerosolization device;
leading the generated aerosol to the focal position of the laser, and simultaneously, positioning the medium containing the alkali metal element at the focal position of the laser;
when the laser interacts with the aerosol, the medium containing the alkali metal elements is ablated at the same time, and the generated plasma contains alkali metal atoms and halogen atoms which are combined to form molecules;
when the fluid to be measured is a gas, the process of forming molecules includes:
leading the gas to the focal position of the laser directly, and simultaneously, positioning the medium containing the alkali metal element at the focal position of the laser;
during the interaction of the laser with the gas, the medium containing the alkali metal element is also ablated, and the plasma generated at this time contains alkali metal atoms and halogen atoms, which combine to form molecules.
Further, the content of the alkali metal element satisfies:
the detected information of the emission spectrum of the molecule can be used for analyzing the kind and content of the halogen element.
The invention has the further beneficial effects that: the mass fraction of the alkali metal elements in the medium is high, the mass fraction of the alkali metal in the used medium containing the alkali metal elements is high, and the plasma generated by ablation contains abundant alkali metal atoms, so that the combination of the alkali metal atoms and halogen atoms in the plasma is promoted, and the high molecular spectrum intensity is obtained.
Further, the detecting the spectral information emitted by the molecule is specifically detecting the spectral information in the visible light region emitted by the molecule.
The invention has the further beneficial effects that: the emission spectrum intensity of molecules formed by halogen elements and alkali metal elements is generally stronger in a visible light region, the emission spectrum line of the molecules formed by combining the halogen elements and the alkali metal elements is generally positioned in the visible light region, the detection efficiency of the existing detector in the visible light region is generally higher, and the detection sensitivity of the halogen elements in the fluid can be effectively improved.
Further, the medium is a solid matrix.
The invention has the further beneficial effects that: compared with liquid and gas, the solid matrix is easy to detect and operate and convenient to operate.
The invention also provides a system for detecting halogen elements in fluid, comprising:
a laser for generating laser light;
the optical path system is used for changing the transmission direction of the laser and focusing the laser;
the medium containing alkali metal elements is used for being ablated at the focal position of the laser together with the fluid to be detected containing halogen elements, the generated plasma simultaneously contains alkali metal atoms in the medium and halogen atoms in the fluid to be detected, and the alkali metal atoms and the halogen atoms are combined to form molecules;
the spectrum detection module is used for collecting light generated by the molecules in the plasma and converting the light into a spectrum;
and the processor is used for analyzing the information of the spectrum to obtain the type and the content of the halogen element in the fluid to be detected.
The invention has the beneficial effects that: the invention provides a detection system of halogen elements in fluid based on laser-induced breakdown spectroscopy, when the fluid containing the halogen elements is ablated by laser generated by a laser, a medium containing alkali metals is ablated at the same time, the generated plasma contains halogen atoms to be detected and abundant alkali metal atoms, molecules formed by combining the halogen elements and the alkali metal elements have strong emission spectrum intensity in a visible light region, a spectrum detection module detects the spectrum emitted by the molecules, and a processor analyzes halogen element information by using the molecular emission spectrum to replace the halogen element atomic emission spectrum adopted by the traditional detection method, so that the problem that the atomic emission spectrum of the halogen elements is weak in the visible light region can be effectively solved, and the real-time online high-sensitivity detection of the halogen elements can be realized. In addition, the system does not increase the complexity and the cost of a laser-induced breakdown spectroscopy device, retains the advantages of high detection speed of the LIBS technology, no limitation of sample types and environments and the like, and can realize real-time online monitoring on the halogen elements in the fluid.
Further, the content of the alkali metal element satisfies:
the detected information of the emission spectrum of the molecule can be used for analyzing the kind and content of the halogen element.
The invention has the further beneficial effects that: the mass fraction of the alkali metal elements in the medium is high, the mass fraction of the alkali metal in the used medium containing the alkali metal elements is high, and the plasma generated by ablation contains abundant alkali metal atoms, so that the combination of the alkali metal atoms and halogen atoms in the plasma is promoted, and the high molecular spectrum intensity is obtained.
Further, the processor specifically analyzes the information of the spectrum by: analyzing the visible region spectral information emitted by the molecule.
The invention has the further beneficial effects that: the emission spectrum intensity of molecules formed by halogen elements and alkali metal elements is generally stronger in a visible light region, the emission spectrum line of the molecules formed by combining the halogen elements and the alkali metal elements is generally positioned in the visible light region, the detection efficiency of the existing detector in the visible light region is generally higher, and the detection sensitivity of the halogen elements in the fluid can be effectively improved.
Further, the medium is a solid matrix.
The invention has the further beneficial effects that: compared with liquid and gas, the solid matrix is easy to detect and operate and convenient to operate.
Further, the spectrum detection module comprises: an optical collection device, an optical fiber, a spectrometer, and a detector;
the optical acquisition device collects molecular optical signals generated by the transition of the molecules in the excited state to the ground state, transmits the molecular optical signals to the spectrometer through the optical fiber to split light, and transmits the split light to the detector, and the detector performs photoelectric conversion, accumulation and amplification on the obtained optical signals to obtain a spectrum for analyzing halogen element information.
Drawings
Fig. 1 is a flow chart of a method for detecting halogen in a fluid according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a system for detecting halogen in a fluid according to an embodiment of the present invention;
FIG. 3 is a diagram of CaF molecular emission spectra of a sodium fluoride solution provided in an embodiment of the present invention;
FIG. 4 is a CaCl molecular emission spectrum of a sodium chloride solution provided in an embodiment of the present invention;
FIG. 5 is a schematic view of another system for detecting halogen in a fluid according to an embodiment of the present invention;
FIG. 6 is a CaF molecular emission spectrum of trifluoromethane provided by the embodiment of the present invention.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:
the device comprises a laser 1, a reflector 2, a focusing lens 3, a solid matrix containing alkali metal elements 4, a three-dimensional displacement platform 5, an acquisition light path 6, an optical fiber 7, a spectrometer 8, a detector 9, a synchronous signal transmission line 10, a USB data transmission line 11, a computer 12, an air atomization device 13, a vent pipe 14 and a gas collection bottle 15.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example one
A method for detecting halogen in a fluid, as shown in fig. 1, includes:
leading the fluid to be tested containing the halogen element into a medium containing an alkali metal element;
the method comprises the following steps of (1) ablating fluid to be detected by laser, simultaneously ablating a medium, wherein plasma generated by laser ablation contains alkali metal atoms and halogen atoms, and the alkali metal atoms and the halogen atoms are combined to form molecules;
and obtaining the type and content of the halogen element in the fluid to be detected by detecting the spectral information emitted by the molecules.
The medium containing the alkali metal element in the method may be a solid, a liquid or a gas.
In addition, when the information analysis of the halogen element is performed based on the spectral information, qualitative and quantitative analysis can be performed. That is, when the solid base containing the alkali metal is used, the emission spectrum band positions of molecules formed by combining different halogen elements in the fluid to be measured and the alkali metal are different, and the halogen element species in the fluid can be obtained. Further, when the solid matrix containing alkali metal is the same, the amount of alkali metal atoms generated by laser ablation of the matrix is the same, when the fluid to be measured containing halogen with different concentrations is ablated by laser, the amount of halogen atoms in plasma is different, the number of molecules formed by combination is also different, different emission spectrum intensities are obtained, and therefore the content of halogen elements in the fluid to be measured is determined
Specifically, for qualitative analysis, a medium is selected, and the actual detection process is performed on the fluid to be detected, wherein the used mediums containing alkali metals are the same for different halogen elements in the fluid to be detected, and the emission spectral band positions of molecules formed by combining different halogen elements in the fluid to be detected and alkali metal elements are different, so that the types of the halogen elements in the fluid can be obtained, and qualitative analysis is realized.
For quantitative analysis, a medium is selected, the actual detection process is carried out on the fluid to be detected, wherein the used mediums containing alkali metals are the same aiming at halogen elements with different concentrations in the fluid to be detected, the quantity of alkali metal atoms generated by laser ablation of the medium is the same, when the fluid to be detected with the halogen with different concentrations is ablated by laser, the quantity of the halogen atoms in the plasma is different, the number of molecules formed by combination is also different, different emission spectrum intensities are obtained, and therefore the content of the halogen elements in the fluid to be detected is determined, and quantitative analysis is achieved.
The embodiment provides a method for detecting halogen elements in fluid based on laser-induced breakdown spectroscopy, wherein when the fluid containing the halogen elements is ablated by laser, a medium containing alkali metals is ablated at the same time, generated plasma contains halogen atoms to be detected and abundant alkali metal atoms, molecules formed by the combination of the halogen elements and the alkali metal elements have strong emission spectrum intensity in a visible light region, and the molecular emission spectrum is used for replacing a halogen element atom emission spectrum adopted by a traditional detection method to analyze halogen element information, so that the problem that the atomic emission spectrum of the halogen elements is weak in the visible light region can be effectively solved, and the high-sensitivity detection of the halogen elements can be realized. In addition, the method does not increase the complexity and the cost of a laser-induced breakdown spectroscopy device, retains the advantages of high detection speed of the LIBS technology, no limitation of sample types and environments and the like, and can realize real-time online monitoring on the halogen elements in the fluid.
Preferably, when the fluid to be measured is a solution, the above process of forming molecules includes:
converting the solution into an aerosol using an aerosolization device; leading the generated aerosol to the focal position of the laser, and simultaneously, positioning the medium containing the alkali metal element at the focal position of the laser; during the interaction of the laser and the aerosol, the medium containing the alkali metal element is also ablated, and the plasma generated at this time contains alkali metal atoms and halogen atoms, which combine to form molecules.
For example, when the medium containing the alkali metal element can be a solid substrate, firstly, a solution containing the halogen element is converted into aerosol by using an aerosol atomization system, then the generated aerosol is led to the focal position of laser, and the surface of the solid substrate containing the alkali metal element is also positioned at the focal plane position of the laser.
When the fluid to be measured is a gas, the process of forming molecules comprises the following steps:
leading the gas to the focal position of the laser directly, and simultaneously, positioning the medium containing the alkali metal element at the focal position of the laser; during the interaction of the laser with the gas, the medium containing the alkali metal element is also ablated, and the plasma generated at this time contains alkali metal atoms and halogen atoms, which combine to form molecules.
For example, when the medium containing the alkali metal element may be a solid substrate, the gas is directly introduced to the focal position of the laser, and the surface of the solid substrate containing the alkali metal element is also located at the focal plane position of the laser, and when the laser interacts with the gas, the solid substrate containing the alkali metal element is also ablated, and the plasma generated at this time contains the alkali metal atom and the halogen atom to be detected, and the alkali metal atom and the halogen atom in the plasma combine to form a stable molecule
Preferably, 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 the halogen element.
On one hand, the mass fraction of the alkali metal element in the medium is high, the mass fraction of the alkali metal in the used medium containing the alkali metal element is high, and the plasma generated by ablation contains abundant alkali metal atoms, so that the combination of the alkali metal atoms and halogen atoms in the plasma is promoted, and the high molecular spectral intensity is obtained; on the other hand, the alkali metal atoms and halogen atoms contained in the plasma need to be combined to form a stable molecule enough to ensure that the intensity of the emission spectrum of the detected molecule can be used for analyzing the type and content of the halogen element. Wherein the term "stable" refers to that the alkali metal atom and the halogen element are combined to form a molecule with high dissociation energy, and the molecule can stably exist in the plasma so as to generate a stronger molecular emission spectrum.
Preferably, the spectral information emitted by the detection molecule is spectral information in a visible light region emitted by the detection molecule.
The emission spectrum intensity of molecules formed by halogen elements and alkali metal elements is generally stronger in a visible light region, the emission spectrum line of the molecules formed by combining the halogen elements and the alkali metal elements is generally positioned in the visible light region, the detection efficiency of the existing detector in the visible light region is generally higher, and the detection sensitivity of the halogen elements in the fluid can be effectively improved.
The ultraviolet spectrum is low in collection efficiency due to factors such as absorption by the environment during collection, and is very high in intensity itself, and therefore, even if absorbed, it is sometimes used for analyzing a halogen element. For the visible light region spectrum, although there may be spectral line interference due to the collection environment, the collection efficiency is low in the ultraviolet spectrum region after all, so the visible light region spectrum can satisfy the analysis of halogen elements. Here, it is preferable to use spectral information in the visible light region, and reliability is high.
Preferably, the medium is a solid matrix.
As mentioned above, the medium containing alkali metal is only required to satisfy the condition that the mass fraction of the alkali metal element is high, and the cost is low.
In addition, compared with liquid and gas, the solid matrix is easy to detect and operate and convenient to operate.
Example two
A system for detecting halogen in a fluid, comprising: the system comprises a laser, an optical path system, a medium containing alkali metal elements, a spectrum detection module and a computer. Wherein the content of the first and second substances,
a laser for generating laser light; the optical path system is used for changing the laser transmission method and focusing the laser transmission method; the medium containing alkali metal elements is used for being ablated at the focal position of laser together with the fluid to be detected containing halogen elements, and the generated plasma simultaneously contains alkali metal atoms in the medium and halogen atoms in the fluid to be detected, and the alkali metal atoms and the halogen atoms are combined to form molecules; the spectrum detection module is used for collecting light generated by the molecules in the plasma and converting the light into a spectrum; and the computer is used for analyzing the information of the spectrum to obtain the type and the content of the halogen element in the fluid to be detected.
When the fluid to be measured is a solution, as shown in fig. 2, the solution to be measured containing halogen element is changed into aerosol through an air atomization device 13 and is transmitted to the upper part of the surface of the solid matrix 4 containing alkali metal element through an air pipe 14, the laser 1 with fixed wavelength emits laser and simultaneously transmits a signal to a detector 9 through a synchronous signal transmission line 10 to prepare to receive a spectrum signal, the laser emitted by the laser 1 with fixed wavelength is firstly reflected by a reflecting mirror 2 and then focused on the surface of the solid matrix 4 containing alkali metal element through a focusing lens 3, when the solid matrix is ablated by the focused laser, the aerosol containing halogen element to be measured is ablated at the same time, at this time, the generated plasma contains halogen atom to be measured and abundant alkali metal atom, the halogen atom and the alkali metal atom are combined to form a molecule, the excited molecule transits to the ground state to generate a molecule emission spectrum, and then the molecule is collected by a collection optical path 6 and is transmitted to 8 through an optical fiber, the light is split by the spectrometer 8 and transmitted to the detector 9, the detector 9 performs photoelectric conversion, accumulation and amplification on the obtained spectrum signal, and the data is transmitted to the computer 12 by the USB data transmission line 11. And finally, the computer 12 processes the received spectral data to obtain the type and content of the halogen element in the solution to be detected.
For example, this method will be described in detail by taking the detection of fluorine and chlorine in an aqueous solution as an example.
NaF aqueous solution containing 50ppm of fluorine element and NaCl aqueous solution containing 50ppm of chlorine element are respectively prepared.
The laser selects Nd: YAG 1064 wavelength laser, and the spectrometer is a SCT320 type C-T structure type spectrometer. CaF molecular emission line 529 and 535nm and CaCl molecular emission line 593.4nm are selected as observation lines.
Calcite is chosen as the solid matrix, which mainly consists of calcium carbonate.
The detection process comprises the following steps:
putting the fluorine-containing solution into an atomization device, atomizing the fluorine-containing solution into an aerosol state, and leading the aerosol state to the position near the upper part of the surface of the calcite substrate;
opening a laser to output laser, wherein the focused laser simultaneously ablates an aerosol solution and a solid matrix, the generated plasma contains fluorine atoms and abundant calcium atoms, and the fluorine atoms and the calcium atoms are combined to form CaF molecules;
and observing the emission spectrum of the plasma to obtain a CaF emission spectrum signal.
The CaCl molecular emission spectrum signal can be obtained by replacing the fluorine-containing element aqueous solution with a chlorine-containing element aqueous solution.
To demonstrate the necessity of the substrate to be rich in alkali elements, the glass slide was chosen as a comparative substrate, as shown in fig. 3, and no CaF molecular emission spectra were observed when only calcite was ablated and the aerosol on the slide was ablated, and a clear calcium fluoride molecular emission spectrum signal was observed only when the sodium fluoride aerosol solution above the calcite substrate was ablated. Figure 4 also shows that a significant calcium chloride molecular emission spectrum signal can be observed only when ablating a sodium chloride aerosol solution over a calcite matrix.
In summary, the method and the system provided by the embodiment can be used for remarkably detecting fluorine and chlorine elements in the solution, and halogen elements such as bromine and iodine can be combined with alkali metal elements such as calcium and barium in the plasma to form stable molecules, so that the method provided by the embodiment is expected to realize high-sensitivity online detection of the halogen elements in the solution.
When the fluid to be measured is gas, as shown in fig. 5, the gas to be measured in the gas collection bottle 15 is transmitted to the upper part of the surface of the solid base 4 containing alkali metal elements through the vent pipe 14, the laser 1 with fixed wavelength emits laser and simultaneously transmits signals to the detector 9 through the synchronous signal transmission line 10 to prepare for receiving spectrum signals, the laser emitted by the laser 1 with fixed wavelength is firstly reflected by the reflector 2 and then focused on the surface of the solid base 4 by the focusing mirror 3, when the solid base is ablated by the focused laser, the gas containing halogen elements to be measured is simultaneously ablated, at this time, the generated plasma contains halogen atoms to be measured and abundant alkali metal atoms, the halogen atoms and the alkali metal atoms are combined to form molecules, the molecules in the excited state transition to the ground state to generate a molecular emission spectrum, then the molecular emission spectrum is collected by the collection optical path 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 photoelectrically converts, accumulates and amplifies the obtained spectral signals, and transmits the data to the computer 12 by the USB data transmission line 11. And finally, the computer processes the received spectral data to obtain the type and the content of the halogen element in the gas to be detected, so as to represent the type and the content of the gas.
For example, to detect trifluoromethane (CHF)3) This method will be described by taking a gas as an example.
Using trifluoromethane gas standard substance.
The laser selects Nd: YAG 1064 wavelength laser, and the spectrograph is an ME5000 type middle step structure spectrograph. And selecting CaF as an observation spectral line.
Calcite, which is mainly composed of calcium carbonate, is selected as the solid matrix.
The detection process comprises the following steps:
the trifluoromethane gas is directly led to the position near the upper part of the surface of the calcite matrix through a vent pipe;
opening a laser to output laser, ablating trifluoromethane and a solid matrix by the focused laser, wherein the generated plasma contains fluorine atoms and abundant calcium atoms, and the fluorine atoms and the calcium atoms are combined to form CaF molecules;
and observing the emission spectrum of the plasma to obtain a CaF emission spectrum signal.
As shown in fig. 6, no CaF molecular spectra were detected when the laser ablated calcite alone, and significant CaF molecular emission spectra were observed when trifluoromethane was passed over the surface of the calcite matrix.
In summary, the method and the system provided by the embodiment can be used for remarkably detecting the fluorine element in the gas, and halogen elements such as chlorine, bromine, iodine and the like can be combined with alkali metal elements such as calcium, barium and the like to form stable molecules in the plasma, so that the method provided by the embodiment is expected to realize high-sensitivity online detection of the halogen elements in the gas.
Preferably, the content of the alkali metal element satisfies: the intensity of the emission spectrum of the detected molecules can be used to analyze the type and content of the halogen element. The related description is the same as the first embodiment, and is not repeated herein.
Preferably, the computer analyzes the information of the spectrum specifically as follows: the visible region spectral information emitted by the molecules is analyzed. The related description is the same as the first embodiment, and is not repeated herein.
Preferably, the medium is a solid matrix. The related description is the same as the first embodiment, and is not repeated herein.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for detecting a halogen element in a fluid, comprising:
leading the fluid to be tested containing the halogen element into a medium containing an alkali metal element;
the fluid to be detected is ablated by laser, the medium is ablated at the same time, plasma generated by laser ablation contains alkali metal atoms and halogen atoms at the same time, and the alkali metal atoms and the halogen atoms are combined to form molecules;
and obtaining the type and the content of the halogen element in the fluid to be detected by detecting the spectral information emitted by the molecules.
2. The method as claimed in claim 1, wherein when the fluid to be tested is a solution, the step of forming molecules comprises:
converting the solution into an aerosol using an aerosolization device;
leading the generated aerosol to the focal position of the laser, and simultaneously, positioning the medium containing the alkali metal element at the focal position of the laser;
when the laser interacts with the aerosol, the medium containing the alkali metal elements is ablated at the same time, and the generated plasma contains alkali metal atoms and halogen atoms which are combined to form molecules;
when the fluid to be measured is a gas, the process of forming molecules includes:
leading the gas to the focal position of the laser directly, and simultaneously, positioning the medium containing the alkali metal element at the focal position of the laser;
during the interaction of the laser with the gas, the medium containing the alkali metal element is also ablated, and the plasma generated at this time contains alkali metal atoms and halogen atoms, which combine to form molecules.
3. The method as claimed in claim 1, wherein the content of alkali metal element is satisfied:
the detected information of the emission spectrum of the molecule can be used for analyzing the kind and content of the halogen element.
4. A method as claimed in any one of claims 1 to 3, wherein the spectral information emitted by the molecule is detected specifically in the visible region.
5. A method as claimed in any one of claims 1 to 3, wherein the medium is a solid substrate.
6. A system for detecting halogen in a fluid, comprising:
a laser for generating laser light;
the optical path system is used for changing the transmission direction of the laser and focusing the laser;
the medium containing alkali metal elements is used for being ablated at the focal position of the laser together with the fluid to be detected containing halogen elements, the generated plasma simultaneously contains alkali metal atoms in the medium and halogen atoms in the fluid to be detected, and the alkali metal atoms and the halogen atoms are combined to form molecules;
the spectrum detection module is used for collecting light generated by the molecules in the plasma and converting the light into a spectrum;
and the processor is used for analyzing the information of the spectrum to obtain the type and the content of the halogen element in the fluid to be detected.
7. The system of claim 6, wherein the alkali metal element is present in an amount sufficient to:
the detected information of the emission spectrum of the molecule can be used for analyzing the kind and content of the halogen element.
8. The system of claim 6, wherein the processor analyzes the spectral information by: analyzing the visible region spectral information emitted by the molecule.
9. The system of claim 6, wherein the medium is a solid substrate.
10. The system of any one of claims 6 to 9, wherein the spectrum detection module comprises: an optical collection device, an optical fiber, a spectrometer, and a detector;
the light collection device collects a molecular light signal generated by the transition of the excited molecule to the ground state, transmits the molecular light signal to the spectrometer through the optical fiber for light splitting, and then transmits the molecular light signal to the detector, and the detector performs photoelectric conversion, accumulation and amplification on the obtained light signal to obtain a spectrum for analyzing halogen element information.
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| PCT/CN2020/138236 WO2022120941A1 (en) | 2020-12-11 | 2020-12-22 | Method and system for detecting halogen element in fluid |
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