Online detection system and method for chemical composition of solid-liquid mixture based on laser multispectral analysis

Abstract

The present invention relates to an online detection system and method for the chemical composition of a solid-liquid mixture based on laser multispectral analysis, comprising: (1) a stable solid-liquid two-phase flow generation module, which provides a uniform and stable solid-liquid two-phase flow column for a measurement module; (2) a laser-induced breakdown spectroscopy measurement module, which detects atomic emission spectra; (3) a laser Raman spectroscopy measurement module, which detects molecular emission spectra; (4) a particle size analysis module, which characterizes particle size information; and (5) a multi-sensor synchronization control and multi-source data fusion processing module, which is responsible for time synchronization of the laser, spectral detector, data storage and processing unit in the system, analysis and processing of multi-source heterogeneous spectral data, and output of the final online chemical composition detection result. The system designed by the present invention is used to perform online detection of solid-liquid mixtures, and can simultaneously analyze the particle size distribution, elemental and mineral composition in the solid-liquid mixture, and obtain higher analysis accuracy through fusion analysis of multi-source heterogeneous data.

Description

Technical Field

[0001] The present invention belongs to the field of physics-measurement-automatic analysis, and in particular relates to an online detection system and method for the chemical composition of a solid-liquid mixture based on laser multispectral analysis. Background Art

[0002] Solid-liquid mixtures are widely present in the natural environment and industrial production. As a crucial material carrier and transport method, they are used in a variety of fields, including mineral production and transportation, petrochemicals, hydrometallurgy, and food and pharmaceutical production. The chemical composition of solid-liquid mixtures is an important parameter for studying their internal state, transport mechanisms, and dynamics. Solid-liquid mixtures are a complex material state, involving the mixing of two distinct phases, solid particles and liquid. The measurement of their chemical composition is influenced by a variety of factors, including particle size distribution, concentration, flow rate, and mineral composition.

[0003] Existing online analytical instruments are usually only suitable for situations where the interference parameters remain unchanged or are only within a very small range. Once the interference changes, the measurement accuracy will decrease. Therefore, they are only used for trend tracking in some production fields. In order to obtain higher measurement accuracy, it is often necessary to go through complex pre-treatment sample preparation processes such as sampling, separation, drying, and grinding to separate various interferences, and then perform chemical analysis. The entire process takes up to several hours, or even days. Since solid-liquid mixtures often involve complex chemical reactions and material transfer processes, this information feedback method with a large lag makes it difficult to reveal the dynamic state change process within them, making it difficult for related production fields to achieve precise modeling and regulation of complex physical and chemical reaction processes. This has become a major bottleneck in the technological development of many process fields such as mineral separation, pharmaceuticals, and environmental engineering.

[0004] In summary, existing analytical instruments and technologies are unable to achieve high-precision online analysis of chemical composition under measurement conditions of complex changes in the physical and chemical matrix, which restricts process innovation and industrial upgrading in the fields of mineral processing, control, and environmental engineering. Summary of the Invention

[0005] In view of the above-mentioned deficiencies of existing analytical instruments and technologies, the purpose of the present invention is to provide a solid-liquid mixture chemical composition analysis system and method that can be applied online, which obtains high-precision chemical component content information through laser multispectral measurement of solid-liquid two-phase flow and fusion analysis of multi-source heterogeneous data.

[0006] The technical solution adopted by the present invention to achieve the above-mentioned purpose is: an online detection system for the chemical composition of solid-liquid mixtures based on laser multispectral analysis, comprising:

[0007] The stable solid-liquid two-phase flow generation module includes an online sampling and stabilizing flow structure and a diversion sampling structure; it is used to obtain stable solid-liquid two-phase flow samples to be tested and introduce the samples to be tested into different measurement modules through the diversion sampling structure;

[0008] The laser-induced breakdown spectroscopy measurement module includes a pulsed laser, a LIBS spectrometer, and a laser excitation and plasma luminescence detection optical system. The module is used to focus the pulsed laser onto the surface of the solid-liquid two-phase flow through the laser excitation and plasma luminescence detection optical system to generate plasma, and to collect the LIBS spectrum using the LIBS spectrometer through the laser excitation and plasma luminescence detection optical system.

[0009] The laser Raman spectroscopy measurement module includes a continuous laser, a Raman spectrometer, and a laser emission and Raman scattered light detection optical system. The laser is focused onto the surface of the solid-liquid two-phase flow through the laser emission and Raman scattered light detection optical system to generate Raman scattering, and the Raman spectra are collected using the Raman spectrometer.

[0010] The particle size analysis module includes a dilution and dispersion structure and a He-Ne laser light source and an optical detector located on either side of the dilution and dispersion structure. The module is used to illuminate the solid-liquid two-phase flow passing through the dilution and dispersion structure with the He-Ne laser light source and measure Mie scattering with the optical detector to obtain solid phase particle size distribution data.

[0011] The multi-sensor synchronous control and multi-source data fusion processing module includes a host computer and a timing generator. The host computer uses the timing generator to realize the timing control of the above modules, synchronously saves the spectrum and particle size data measured by each module, performs analysis and calculation, and outputs the chemical composition analysis results.

[0012] The laser-induced breakdown spectroscopy measurement module is configured, depending on specific application requirements, with 1) a single or dual pulsed lasers (with wavelengths of 355 nm, 532 nm, or 1064 nm) as the excitation light source; 2) a spectrometer with different detection bands or a combination of multiple spectrometers to detect LIBS spectral signals in the extreme ultraviolet to near-infrared wavelength range; and 3) a coaxial or non-coaxial optical system for laser excitation and plasma luminescence detection.

[0013] The laser Raman spectroscopy measurement module is configured according to specific application requirements: 1) a laser with a wavelength of 532nm, 785nm or 1064nm and a spectrometer with a spectral band corresponding to the laser wavelength; 2) the laser emission and Raman scattered light detection optical system used for laser incidence and Raman spectrum collection is a coaxial or non-coaxial optical system.

[0014] The laser excitation and plasma luminescence detection optical system and the laser emission and Raman scattered light detection optical system are two completely independent optical systems, or a comprehensive optical system that reuses some components.

[0015] The dilution and dispersion structure includes a mixing barrel, on which a solid-liquid two-phase flow injection pipeline, a clean water injection pipeline, a measurement output pipeline, and a drainage pipeline are provided. An agitator is provided at the bottom of the barrel, a shading ratio detector is provided on the barrel wall, and the measurement output pipeline is connected to the measurement window.

[0016] The online detection method for the chemical composition of solid-liquid mixtures based on laser multispectral analysis includes the following measurement and analysis steps: collecting spectral data, establishing a multispectral fusion analysis model, and online detection. The method is used for online real-time analysis and measurement of different solid-liquid mixtures. The method includes the following steps:

[0017] Step 1: The host computer of the multi-sensor synchronization control and multi-source data fusion processing module controls the timing generator to output multiple trigger signals with different delays, respectively controlling the laser induced breakdown spectroscopy measurement module, laser Raman spectroscopy measurement module, and particle size analysis module to collect multi-source heterogeneous data of the same time sequence for each solid-liquid two-phase flow sample in the modeling sample set: LIBS spectrum, Raman spectrum, and solid phase particle size distribution data;

[0018] Step 2: The host computer integrates multi-source heterogeneous data to perform chemical composition modeling and analysis. This involves using the LIBS spectra, Raman spectra, and particle size data of all solid-liquid two-phase flow samples in the modeling sample set as input, and the content of each element and compound in the solid-liquid two-phase flow as output to construct a chemical composition analysis model.

[0019] Step 3: Multi-source heterogeneous data of the solid-liquid two-phase flow sample to be tested are collected in real time under the same time sequence, input into the chemical composition analysis model for solution, and the content of the elements and compounds to be tested is output in real time.

[0020] The collecting of multi-source heterogeneous data includes:

[0021] Step 11: The laser-induced breakdown spectroscopy measurement module receives the trigger command, controls the pulsed laser to output pulsed laser, focuses the laser on the surface of the solid-liquid two-phase flow through the laser excitation and plasma luminescence detection optical system to generate plasma, and controls the LIBS spectrometer to collect LIBS spectra through the laser excitation and plasma luminescence detection optical system;

[0022] Step 12: The laser Raman spectroscopy measurement module receives the trigger command, controls the continuous laser to output laser light, focuses the laser light onto the surface of the solid-liquid two-phase flow through the laser emission and Raman scattered light detection optical system to generate Raman scattering, and controls the Raman spectrometer to collect Raman spectra through the laser emission and Raman scattered light detection optical system;

[0023] Step 13: The particle size analysis module receives the trigger instruction, controls the He-Ne laser light source to irradiate the solid-liquid two-phase flow passing through the dilution and dispersion structure, collects the Mie scattering spectrum information obtained on the optical detector, and calculates the solid phase particle size distribution data.

[0024] The particle size analysis module collects solid phase particle size distribution data including the following steps:

[0025] Step 13a: The host computer controls a portion of the original solid-liquid two-phase flow diverted by the diversion sampling structure to be injected into the mixing barrel through the solid-liquid two-phase flow injection pipeline, controls the agitator to stir uniformly, and controls the clean water injection pipeline to inject clean water for dilution, thereby adjusting the shading ratio of the solid-liquid mixture in the mixing barrel;

[0026] Step 13b: When the shading ratio detector detects that the shading ratio value is suitable for particle size measurement, the injection of the solid-liquid two-phase flow injection pipeline and the clean water injection pipeline is stopped, and the measurement output pipeline is controlled to open to introduce the solid-liquid mixture into the measurement window for laser particle size measurement;

[0027] Step 13c: After the measurement is completed, the drainage pipeline and the clean water injection pipeline are controlled to open, the solid-liquid two-phase flow is emptied and the mixing barrel and the measurement window are cleaned.

[0028] The chemical composition analysis model is:

[0029] C x =f(I LIBS ,I Raman ,I Mie )

[0030] Where x is an atom (element) or molecule (compound), I LIBS , I Raman and I Mie are LIBS spectrum, Raman spectrum and Mie scattering spectrum data respectively. f(·) is the chemical composition quantitative analysis model established by the supervised learning method. The modeling samples are solid-liquid two-phase flow samples with known chemical composition. The training data are the multispectral measurement data of each modeling sample. The response label is the chemical composition content information.

[0031] The LIBS spectrum and Raman spectrum data I LIBS and I Raman , which is the original spectral data collected by the spectrometer, or the spectral feature data after data preprocessing and feature extraction;

[0032] The Mie scattering spectrum data I Mie , which is the scattering spectrum intensity data at different positions collected by the spectral detector, or the particle size distribution data calculated by the laser particle size analyzer based on the scattering spectrum.

[0033] The present invention has the following advantages and beneficial effects:

[0034] 1. The online chemical composition analysis system proposed in this paper simultaneously measures LIBS spectra, Raman spectra, and Mie scattering spectra. By configuring lasers of different wavelengths, spectrometers of different spectral bands, and detectors at different angles, it can characterize the physicochemical composition of different substances at the atomic, molecular, and particle scales. It can be widely used for online analysis of the chemical composition of various solid-liquid mixtures.

[0035] 2. The present invention can realize the simultaneous analysis of the atomic and molecular composition of solid-liquid mixtures by fusing and analyzing heterogeneous data from multiple sensors, and can eliminate the complex influence of changes in the atomic, molecular composition and particle size of solid-liquid mixtures on spectral signals during online measurement, thereby realizing high-precision online analysis of chemical composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 Schematic diagram of an online detection system for the chemical composition of solid-liquid mixtures based on laser multispectral analysis;

[0037] Figure 2 Schematic diagram of online sampling, flow stabilization and flow diversion structure;

[0038] Figure 3 Schematic diagram of the optical system and spectrum splicing of the laser-induced breakdown spectroscopy measurement module;

[0039] Figure 4 This is a schematic diagram of the dilution and dispersion structure of the laser particle size analysis module;

[0040] Figure 5 This is a schematic diagram of the modeling and application of the multispectral fusion analysis model;

[0041] Among them, 1 is a stable solid-liquid two-phase flow generation module, 11 is an online sampling and steady flow structure, 1101 is a feeding component, 1102 is a stirring barrel, 1103 is a stirrer, 1104 is a control valve, 1105 is a steady flow box, 1106 is a solid-liquid two-phase flow outlet, 12 is a diversion sampling structure, 2 is a laser induced breakdown spectroscopy measurement module, 21 is a pulsed laser, 22 is a LIBS spectrometer, 23 is a laser excitation and plasma luminescence detection optical system, 2301 is a laser beam expansion optical path, 2302 is a plasma luminescence detection optical path, 2303 is a coaxial coupling focusing optical path, 3 is a laser Raman spectroscopy measurement module, 31 is Continuous laser, 32 is a Raman spectrometer, 33 is a laser emission and Raman scattered light detection optical system, 4 is a laser particle size analysis module, 41 is a dilution and dispersion structure, 4101 is a mixing barrel, 4102 is a solid-liquid two-phase flow injection pipeline, 4103 is a clean water injection pipeline, 4104 is a measurement output pipeline, 4105 is a drainage pipeline, 4106 is an agitator at the bottom of the barrel, 4107 is a shading ratio detector at the barrel wall, 4108 is a connection measurement window, 42 is a helium-neon laser light source, 43 is an optical detector, 5 is a multi-sensor synchronization control and multi-source data fusion processing module, 51 is a host computer, and 52 is a timing generator. DETAILED DESCRIPTION

[0042] To make the above-mentioned objects, features, and advantages of the present invention more readily apparent, the specific implementation methods of the present invention are described in detail below with reference to the accompanying drawings. The following description sets forth many specific details to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art may make similar modifications without departing from the scope of the invention. Therefore, the present invention is not limited to the specific implementation methods disclosed below.

[0043] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. The terms used in the specification of the invention herein are for the purpose of describing specific embodiments only and are not intended to limit the present invention.

[0044] The online detection system for the chemical composition of solid-liquid mixtures based on laser multispectral analysis specifically includes: a stable solid-liquid two-phase flow generation module 1, a laser-induced breakdown spectroscopy measurement module 2, a laser Raman spectroscopy measurement module 3, a laser particle size analysis module 4, and a multi-sensor synchronization control and multi-source data fusion processing module 5. The stable solid-liquid two-phase flow generation module 1 generates a stable solid-liquid two-phase flow sample to be tested through an online sampling and flow stabilization structure 11, and then directs the sample to be tested into different measurement modules 2, 3, and 4 through a diversion sampling structure 12.

[0045] The stable solid-liquid two-phase flow generation module 1 includes an online sampling and stabilizing flow structure 11 and a diverter sampling structure 12. The online sampling and stabilizing flow structure 11 utilizes the automatic slurry stirring and distribution feeding system described in patent CN115155385A, which includes a feeding assembly 1101, a stirring barrel 1102, an agitator 1103, a slurry valve 1104, a flow stabilizing box 1105, and an outlet 1106. The present invention adds a diverter sampling structure 12 below outlet 1106 to generate two paths: one path directs a portion of the solid-liquid two-phase flow through a pipeline to the particle size analysis module 4; the other path retains the majority of the remaining solid-liquid two-phase flow and flows vertically downward for measurement by the laser-induced breakdown spectroscopy measurement module 2 and the laser Raman spectroscopy measurement module 3. The online sampling and flow stabilization structure 11 forms a uniform and stable solid-liquid two-phase flow of the solid-liquid mixture only through operations such as stirring and stabilizing the flow. The diverter sampling structure 2 adopts a diverter valve to proportionally introduce the solid-liquid two-phase flow into the particle size measurement module 4 and the spectral measurement modules 2 and 3. While providing a representative solid-liquid mixture sample for measurement to the particle size measurement module 4, it provides a vertically flowing stable liquid column for the laser induced breakdown spectroscopy measurement module 2 and the Raman spectroscopy measurement module 3 directly for spectral measurement, without the need for sample pre-processing such as sampling, reduction, and drying before measurement.

[0046] The laser induced breakdown spectroscopy measurement module 2 includes a pulse laser 21, a LIBS spectrometer 22, and a laser excitation and plasma luminescence detection optical system 23. In the laser induced breakdown spectroscopy measurement module 2, i) the pulse laser 21 can be configured with a single or two pulse lasers according to specific application requirements, and the laser wavelength can be 355nm, 532nm or 1064nm; ii) the LIBS spectrometer 22 can select a single spectrometer with different detection spectral bands or a plurality of spectrometers spliced ​​together to detect LIBS spectral signals within the extreme ultraviolet-near infrared wavelength range. Splicing of multiple spectrometers refers to directing plasma luminescence into spectrometers with different spectral bands through a one-to-many optical fiber, and splicing the spectra detected by each spectrometer into a spectrum according to wavelength, such as Figure 3 iii) The laser excitation and spectral signal acquisition of the laser excitation and plasma luminescence detection optical system 23 is realized by a coaxial or non-coaxial optical system. The laser excitation and plasma luminescence detection optical system 23 includes the following Figure 3 As shown, the laser beam expansion optical path 2301, the plasma luminescence detection optical path 2302 and the coaxial coupling focusing optical path 2303, the pulse laser 21 focuses the laser onto the surface of the solid-liquid two-phase flow through the laser excitation and plasma luminescence detection optical system 23's laser beam expansion optical path 2301 and the coaxial coupling focusing optical path 2302 to generate plasma, and the LIBS spectrometer 22 collects the LIBS spectrum through the laser excitation and plasma luminescence detection optical system 23's plasma luminescence detection optical path 2302 and the coaxial coupling focusing optical path 2303.

[0047] The laser Raman spectroscopy measurement module 3 includes a continuous laser 31, a Raman spectrometer 32, and a laser emission and Raman scattered light detection optical system 33. Laser light emitted by the continuous laser 31 is directed onto the surface of the solid-liquid two-phase flow via the laser emission and Raman scattered light detection optical system 33, and the Raman scattered light spectrum is collected using the Raman spectrometer 32. In the laser Raman spectroscopy measurement module 3, i) the continuous laser 31 can be configured with a wavelength of 532nm, 785nm, or 1064nm, depending on the specific application requirements; ii) the Raman spectrometer 33 selects the spectral range corresponding to the laser wavelength; and iii) laser injection and spectrum collection by the laser emission and Raman scattered light detection optical system 33 are achieved through coaxial or non-coaxial optical systems.

[0048] The laser excitation and plasma luminescence detection optical system 23 and the laser emission and Raman scattered light detection optical system 33 described in the laser induced breakdown spectroscopy measurement module 2 and the laser Raman spectroscopy measurement module 3 can be two completely independent optical systems or a comprehensive optical system that reuses some components.

[0049] The laser particle size analysis module 4 includes a dilution and dispersion structure 41 and a helium-neon laser light source 42 and an optical detector 43 respectively arranged on both sides of the dilution and dispersion structure 41. Figure 4 As shown, it includes: a mixing barrel 4101, a solid-liquid two-phase flow injection pipeline 4102, a clean water injection pipeline 4103, a measurement output pipeline 4104, and a drainage pipeline 4105 are provided on the barrel body, an agitator 4106 is provided at the bottom of the barrel, a shading ratio detector 4107 is provided on the barrel wall, and the measurement output pipeline 4104 is connected to the measurement window 4108. A portion of the original solid-liquid two-phase flow drained by the diversion sampling structure 12 is injected into the mixing barrel 4101 through the solid-liquid two-phase flow injection pipe 4102, stirred and kept uniform by the agitator 4106, and diluted by injecting clean water through the clean water injection pipe 4103, thereby adjusting the shading ratio of the solid-liquid mixture in the mixing barrel 4101. When the shading ratio detector 4107 detects that the shading ratio value is suitable for particle size measurement, the injection of the solid-liquid two-phase flow injection pipe 4102 and the clean water injection pipe 4103 is stopped, and the measurement output pipe 4104 is opened to guide the solid-liquid mixture into the measurement window 4108 for laser particle size measurement. After the measurement is completed, the drain pipe 4105 and the clean water injection pipe 4103 are opened to drain the solid-liquid two-phase flow and clean the mixing barrel 4101 and the measurement window 4108. During laser particle size measurement, a helium-neon laser source 42 illuminates the solid-liquid two-phase flow sample through a measurement window 4108. Optical detector 43, located on the other side of measurement window 4108, detects and collects the Mie scattering spectrum of the helium-neon laser source 42 after it passes through 41, obtaining particle size information. The particle size data output by optical detector 43 can be either raw Mie scattering spectrum data or particle size distribution data calculated using the Mie scattering spectrum.

[0050] The multi-sensor synchronous control and multi-source data fusion processing module 5 includes a host computer 51 and a timing generator 52. The host computer 51 uses the timing generator 52 to implement timing control of the other modules, synchronously measure and store the spectral data of each module, perform analysis and calculations, and output chemical composition analysis results. In the multi-sensor synchronous control and multi-source data fusion processing module 5, the timing generator 52 can provide multiple trigger signals. While measuring particle size information, it sequentially triggers the Raman laser, Raman spectrometer, LIBS laser, and LIBS spectrometer with different delays, ensuring that the laser spectral measurements of different modules are performed synchronously. The collected LIBS and Raman spectra correspond to the solid-liquid two-phase flow samples passing through the system during the same time period.

[0051] The laser-induced breakdown spectroscopy measurement module 2 and laser Raman spectroscopy measurement module 3 are only responsible for collecting spectral data and do not perform chemical composition analysis based on LIBS or Raman spectroscopy. Quantitative analysis of the atomic and molecular composition of the solid-liquid two-phase flow is achieved through the multi-spectral fusion analysis model integrated in the host computer 52 described in the multi-sensor synchronous control and multi-source data fusion processing module 5. The multi-spectral fusion analysis model takes as input the LIBS spectrum, Raman spectrum, and Mie scattering spectrum, and outputs the content of each element and compound in the solid-liquid two-phase flow, namely:

[0052] C x =f(I LIBS ,I Raman ,I Mie )

[0053] Where x is an atom (element) or molecule (compound); I LIBS and I Raman It can be the original spectral data collected by the spectrometer, or it can be the spectral feature data after data preprocessing and feature extraction; I Mie It can be the scattering spectrum intensity data collected by the spectral detector at different positions, or it can be the particle size distribution data calculated based on the scattering spectrum. f(·) is the chemical composition quantitative analysis model established by the supervised learning method. The modeling samples are solid-liquid two-phase flow samples with known chemical composition. The training data are the multispectral measurement data of each modeling sample, and the response label is the chemical composition content information.

[0054] The online detection method of the chemical composition of solid-liquid mixture based on laser multispectral analysis is as follows:

[0055] First, use Figure 1 The online detection system shown here performs simultaneous LIBS, Raman, and Mie scattering measurements on a modeled sample with known chemical composition. The measurement data are used to establish a quantitative chemical composition analysis model. The specific process is as follows:

[0056] 1. Perform the following steps S1-S4 on each modeling sample to obtain the Raman spectrum, LIBS spectrum and particle size data of each sample;

[0057] S1: Import the modeled sample into the online sampling and steady flow structure 11 to generate a top-down steady solid-liquid two-phase flow;

[0058] S2-1: The host computer 53 controls the laser Raman spectroscopy measurement module 3 through the timing generator 52, and focuses the 785 nm laser emitted by the continuous laser 31 vertically onto the surface of the solid-liquid two-phase flow through the laser emission and Raman scattered light detection optical system 33, and uses the Raman spectrometer 32 to collect 200 cm -1 ~3500cm -1 The Raman scattering spectrum of Raman0 , save to the host computer 51;

[0059] S2-2: Call the Raman characteristic peak recognition algorithm on the host computer 51 to find Spc Raman0 The Raman characteristic peaks in the image are calculated and the peak area is saved as I Raman0 ;

[0060] S3-1: The host computer 51 controls the laser-induced breakdown spectroscopy measurement module 2 through the timing generator 52. The 1064 nm laser emitted by the pulsed laser 21 is vertically focused onto the surface of the solid-liquid two-phase flow through the laser excitation and plasma luminescence detection optical system 23 to generate plasma. The LIBS spectrometer 22 is then used to collect the LIBS spectrum in the wide spectral range of 250 to 800 nm, which is recorded as Spc. LIBS0 , save to the host computer 51;

[0061] S3-2: Call the LIBS characteristic spectrum line recognition algorithm on the host computer 51 to find Spc LIB0S Calculate the LIBS characteristic line intensity and save it as I LIBS0 ;

[0062] S4: The sample to be tested is introduced into the laser particle size analysis module 4 through the diversion sampling structure 12. Figure 4 The dilution and dispersion structure 41 shown obtains a sample to be measured with an appropriate light shielding ratio, introduces it into the sample measurement window 4108, records the Mie scattering spectrum formed on the optical detector 43 after the He-Ne laser light source 42 passes through the sample measurement window 4108, obtains the particle size distribution information D0 and saves it to the host computer 51;

[0063] Second, modeling: using each sample’s Raman spectrum, LIBS spectrum, and particle size data to iteratively train the model and obtain the ideal model;

[0064] S5: Align I by timestamp LIBS0, I Raman0 and D0, and integrated into the modeling data training set feature matrix Features0;

[0065] S6: Through supervised learning method, the feature matrix Features0 is used as input data and the known chemical component content is used as reference label to train the quantitative analysis model f(·) of chemical component content.

[0066] 3. Use the ideal model to make actual predictions;

[0067] Afterwards, you can use Figure 1 The online detection system and the established quantitative analysis model are used to perform online analysis of the chemical composition of the solid-liquid mixture to be tested. The specific process is as follows:

[0068] T1: The sample to be tested is introduced into the online sampling and steady flow structure 11 to obtain a stable solid-liquid two-phase flow from top to bottom;

[0069] T2-1: The host computer 51 controls the laser Raman spectroscopy measurement module 3 through the timing generator 52. The 785 nm laser emitted by the continuous laser 31 is vertically focused onto the surface of the solid-liquid two-phase flow through the laser emission and Raman scattered light detection optical system 33. The Raman spectrometer 32 is used to collect 200 cm -1 ~3500cm -1 The Raman scattering spectrum of Raman , save to the host computer 51;

[0070] T2-2: Call the Raman characteristic peak recognition algorithm on the host computer 51 to find Spc Raman The Raman characteristic peaks in the image are calculated and the peak area is saved as I Raman ;

[0071] T3-1: The host computer 51 controls the laser-induced breakdown spectroscopy measurement module 2 through the timing generator 52. The 1064 nm laser emitted by the pulsed laser 21 is vertically focused onto the surface of the solid-liquid two-phase flow through the laser excitation and plasma luminescence detection optical system 23 to generate plasma. The LIBS spectrometer 22 is then used to collect the LIBS spectrum in the wide spectral range of 250 to 800 nm, which is recorded as Spc. LIBS , save to the host computer 51;

[0072] T3-2: Call the LIBS characteristic spectrum line recognition algorithm on the host computer 51 to find Spc LIBS Calculate the LIBS characteristic line intensity and save it as I LIBS ;

[0073] T4: The sample to be tested is introduced into the laser particle size analysis module 4 through the diversion sampling structure 12. After the sample to be tested is obtained through the dilution and dispersion structure 41 with an appropriate light shielding ratio, laser particle size analysis is performed to obtain particle size distribution information D and save it to the host computer 51;

[0074] T5: I LIBS , I Raman And D are integrated into the data feature vector Features;

[0075] T6: The host computer 51 calls the quantitative analysis model f(·) of chemical composition content, substitutes the feature vector Features, and calculates the chemical composition content C of the sample to be tested. x =f(Features).

[0076] The present invention is described above by way of example in conjunction with the accompanying drawings. The present invention is not limited to the above embodiments. As long as various non-substantial improvements are made using the method concepts and technical solutions of the present invention, or the concepts and technical solutions of the invention are directly applied to other occasions without improvement, they are all within the scope of protection of the present invention.

Claims

1. An online detection system for the chemical composition of solid-liquid mixtures based on laser multispectral analysis, characterized in that: include: A stable solid-liquid two-phase flow generation module (1) includes an online sampling and flow stabilization structure (11) and a diversion sampling structure (12); It is used to obtain stable solid-liquid two-phase flow samples to be tested, and to introduce the samples to be tested into different measurement modules through the split flow sampling structure; The laser induced breakdown spectroscopy measurement module (2) comprises a pulse laser (21), a LIBS spectrometer (22), and a laser excitation and plasma luminescence detection optical system (23); the module is used to focus the pulse laser onto the surface of the solid-liquid two-phase flow through the laser excitation and plasma luminescence detection optical system (23) to generate plasma, and to collect the LIBS spectrum through the laser excitation and plasma luminescence detection optical system (23) using the LIBS spectrometer (22); The laser Raman spectroscopy measurement module (3) includes a continuous laser (31), a Raman spectrometer (32), and a laser emission and Raman scattered light detection optical system (33); the laser is focused onto the surface of the solid-liquid two-phase flow by the laser emission and Raman scattered light detection optical system (33) to generate Raman scattering, and the Raman spectrometer (32) is used to collect the Raman spectrum; The particle size analysis module (4) comprises a dilution and dispersion structure (41) and a helium-neon laser light source (42) and an optical detector (43) respectively arranged on both sides thereof; the module is used to irradiate the solid-liquid two-phase flow flowing through the dilution and dispersion structure (41) with the helium-neon laser light source (42), measure Mie scattering with the optical detector (43), and obtain solid phase particle size distribution data; The multi-sensor synchronous control and multi-source data fusion processing module (5) includes a host computer (51) and a timing generator (52); the host computer (51) realizes timing control of the above modules through the timing generator (52), synchronously saves the spectrum and particle size data measured by each module, performs analysis and calculation, and outputs the chemical composition analysis results.

2. The on-line detection system for chemical composition of solid-liquid mixture based on laser multispectral analysis according to claim 1, characterized in that: The laser induced breakdown spectroscopy measurement module (2) is configured with 1) a single or two pulsed lasers according to specific application requirements, and the laser wavelength can be 355nm, 532nm or 1064nm, as an excitation light source; 2) a spectrometer with different detection spectrum bands or a combination of multiple spectrometers is selected to detect LIBS spectrum signals in the extreme ultraviolet-near infrared wavelength range; 3) the laser excitation and plasma luminescence detection optical system (23) is a coaxial or non-coaxial optical system.

3. The on-line detection system for chemical composition of solid-liquid mixture based on laser multispectral analysis according to claim 1, characterized in that: The laser Raman spectrum measurement module (3) is configured with 1) a laser with a wavelength of 532nm, 785nm or 1064nm and a spectrometer with a spectrum band corresponding to the laser wavelength according to specific application requirements; 2) the laser emission and Raman scattered light detection optical system (33) used for laser incidence and Raman spectrum collection is a coaxial or non-coaxial optical system.

4. The on-line detection system for the chemical composition of a solid-liquid mixture based on laser multispectral analysis according to any one of claims 1 to 3, characterized in that: The laser excitation and plasma luminescence detection optical system (23) and the laser emission and Raman scattered light detection optical system (33) are two completely independent optical systems, or a comprehensive optical system that reuses some components.

5. The on-line detection system for chemical composition of solid-liquid mixture based on laser multispectral analysis according to claim 1, characterized in that: The dilution and dispersion structure (41) comprises a mixing barrel (4101), the barrel body being provided with a solid-liquid two-phase flow injection pipeline (4102), a clean water injection pipeline (4103), a measurement output pipeline (4104), and a drainage pipeline (4105); an agitator (4106) being provided at the bottom of the barrel; a light shielding ratio detector (4107) being provided on the barrel wall; and the measurement output pipeline (4104) being connected to a measurement window (4108).

6. An online detection method for the chemical composition of a solid-liquid mixture based on laser multispectral analysis, characterized in that: The following measurement and analysis steps are used to collect spectral data, establish a multi-spectral fusion analysis model, and perform online detection for online real-time analysis and measurement of different solid-liquid mixtures. The method includes the following steps: Step 1: The host computer (51) of the multi-sensor synchronous control and multi-source data fusion processing module (5) controls the timing generator (52) to output multi-channel trigger signals through different delays, respectively controlling the laser induced breakdown spectroscopy measurement module (2), the laser Raman spectroscopy measurement module (3), and the particle size analysis module (4) to collect multi-source heterogeneous data of the same time sequence for each solid-liquid two-phase flow sample in the modeling sample set: LIBS spectrum, Raman spectrum, and solid phase particle size distribution data; Step 2: The host computer (51) fuses multi-source heterogeneous data to perform chemical composition modeling and analysis, including taking the LIBS spectra, Raman spectra and particle size data of all solid-liquid two-phase flow samples in the modeling sample set as input and the contents of each element and compound in the solid-liquid two-phase flow as output to construct a chemical composition analysis model; Step 3: Multi-source heterogeneous data of the solid-liquid two-phase flow sample to be tested are collected in real time under the same time sequence, input into the chemical composition analysis model for solution, and the content of the elements and compounds to be tested is output in real time.

7. The method for online detection of chemical composition of solid-liquid mixture based on laser multispectral analysis according to claim 6, characterized in that: The collecting of multi-source heterogeneous data includes: Step 11: The laser induced breakdown spectroscopy measurement module (2) receives a trigger instruction, controls the pulse laser (21) to output a pulse laser, focuses the laser on the surface of the solid-liquid two-phase flow through the laser excitation and plasma luminescence detection optical system (23) to generate plasma, and controls the LIBS spectrometer (22) to collect the LIBS spectrum through the laser excitation and plasma luminescence detection optical system (23); Step 12: The laser Raman spectrum measurement module (3) receives a trigger instruction, controls the continuous laser (31) to output laser light, focuses the laser light onto the surface of the solid-liquid two-phase flow through the laser emission and Raman scattered light detection optical system (33) to generate Raman scattering, and controls the Raman spectrometer (32) to collect Raman spectra through the laser emission and Raman scattered light detection optical system (33); Step 13: The particle size analysis module (4) receives a trigger instruction, controls the helium-neon laser light source (42) to irradiate the solid-liquid two-phase flow flowing through the dilution and dispersion structure (41), collects Mie scattering spectrum information obtained on the optical detector (43), and calculates the solid phase particle size distribution data.

8. The method for online detection of chemical composition of solid-liquid mixture based on laser multispectral analysis according to claim 7, characterized in that: The particle size analysis module (4) collects solid phase particle size distribution data and comprises the following steps: Step 13a: The host computer (51) controls a portion of the original solid-liquid two-phase flow diverted by the diversion sampling structure (12) to be injected into the mixing barrel (4101) through the solid-liquid two-phase flow injection pipeline (4102), controls the agitator (4106) to stir and maintain uniformity, and controls the clean water injection pipeline (4103) to inject clean water for dilution, thereby adjusting the shading ratio of the solid-liquid mixture in the mixing barrel (4101); Step 13b: When the shading ratio detector (4107) detects that the shading ratio value is suitable for particle size measurement, the injection of the solid-liquid two-phase flow injection pipeline (4102) and the clean water injection pipeline (4103) is stopped, and the measurement output pipeline (4104) is controlled to open to guide the solid-liquid mixture into the measurement window (4108) for laser particle size measurement; Step 13c: After the measurement is completed, the drainage pipeline (4105) and the clean water injection pipeline (4103) are controlled to open, the solid-liquid two-phase flow is emptied and the mixing barrel (4101) and the measurement window (4108) are cleaned.

9. The method for online detection of chemical composition of solid-liquid mixture based on laser multispectral analysis according to claim 6, characterized in that: The chemical composition analysis model is: C x =f(I LIBS ,I Raman ,I Mie ) Where x is an atom (element) or molecule (compound), I LIBS , I Raman and I Mie are LIBS spectrum, Raman spectrum and Mie scattering spectrum data respectively. f(·) is the chemical composition quantitative analysis model established by the supervised learning method. The modeling samples are solid-liquid two-phase flow samples with known chemical composition. The training data are the multispectral measurement data of each modeling sample. The response label is the chemical composition content information.

10. The method for online detection of chemical composition of solid-liquid mixture based on laser multispectral analysis according to claim 9, characterized in that: The LIBS spectrum and Raman spectrum data I LIBS and I Raman , which is the original spectral data collected by the spectrometer, or the spectral feature data after data preprocessing and feature extraction; The Mie scattering spectrum data I Mie , which is the scattering spectrum intensity data at different positions collected by the spectral detector, or the particle size distribution data calculated by the laser particle size analyzer based on the scattering spectrum.

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