CN108760723B - Detection method of portable element analyzer for field survey - Google Patents

Detection method of portable element analyzer for field survey Download PDF

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CN108760723B
CN108760723B CN201810503320.7A CN201810503320A CN108760723B CN 108760723 B CN108760723 B CN 108760723B CN 201810503320 A CN201810503320 A CN 201810503320A CN 108760723 B CN108760723 B CN 108760723B
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sample
filter
light path
control system
light
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CN108760723A (en
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郑培超
曾笑波
王金梅
巩亚明
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Chongqing University of Post and Telecommunications
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/66Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
    • G01N21/67Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using electric arcs or discharges
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/73Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/01Arrangements or apparatus for facilitating the optical investigation
    • G01N2021/0106General arrangement of respective parts
    • G01N2021/0112Apparatus in one mechanical, optical or electronic block

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Abstract

The invention discloses a detection method of a portable element analyzer for field survey, which comprises the following steps: the system comprises a sample introduction system, an electrolyte discharge plasma generation system, a light path collection, filtering and sorting system, a data processing system and a control system; sample injection system introduces electrolyte discharge plasma production system with the sample and carries out glow discharge and send the element spectrum, by the light path is collected and is selected separately the system collection and pass to data processing system with filtering, at last by control system shows and gathers, control system control sample injection system, electrolyte discharge plasma production system, light path are collected and are filtered and select separately system and data processing system. The invention provides a metal element analysis device which does not need to acidify a sample in advance, does not need carrier gas, has more stable discharge, simple and convenient operation, cheap equipment and smaller volume. The detection method disclosed by the invention has the advantages of automatic detection, simplicity in operation and strong field adaptability, and greatly improves the field detection speed and precision.

Description

Detection method of portable element analyzer for field survey
Technical Field
The invention relates to a metal element analysis device, in particular to a detection method of a portable element analyzer, which is used for online detection of a liquid sample, and has the advantages of small volume, low cost and simple and convenient operation.
Background
In the aspect of detecting metal elements in water, the traditional detection methods such as a complex titration method, an electrochemical method, an inductively coupled atomic emission spectrometry and the like often have the defects or shortcomings, and the defects are particularly represented as large equipment volume, high price, complex pretreatment operation and difficulty in realizing real-time continuous detection of the metal elements in the water, and the electrolyte glow discharge technology which is established in recent years can just make up for the defects. The basic structure is as follows: the electrolyte solution is led out through one end of a vertical conduit by a sample introduction device to form a fountain, and a certain positive voltage is applied to the vicinity above the leading-out end by a metal electrode, so that discharge plasma is generated. Webb and the like improve a discharge system from the aspects of reducing the surface area of a cathode, reducing the volume of plasma and the like, and adopt a J-shaped flow guide structure, so that the volume of a sample required by the discharge of the constructed system is reduced, the power of an external circuit is reduced, and the detection capability of the system on metal elements is greatly improved and can reach mu g/L or below.
However, in the research aspect of the electrolyte glow discharge technology, the spectrum detection part of the electrolyte glow discharge technology is collected and processed by a spectrometer, for example, a combined spectrometer which adopts a monochromatic spectrometer and a photomultiplier as a detector or a portable spectrometer is adopted, so that the whole set of detection equipment has large volume and high cost, the portability of a metal ion detection instrument depending on the electrolyte glow discharge principle is reduced, and the electrolyte discharge photoelectric detection technology is limited to be widely applied.
Disclosure of Invention
The invention aims to provide a portable metal element detection device and a detection method thereof aiming at the technical defects in the prior art.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a detection method adopting a portable element analyzer for field survey comprises a sample introduction system, an electrolyte discharge plasma generation system, a light path collection, light filtering and sorting system, a data processing system and a control system; the sample introduction system introduces a sample into the electrolyte discharge plasma generation system to perform glow discharge to emit an element spectrum, the element spectrum is collected by the light path collection and filtering sorting system and transmitted to the data processing system, and finally the element spectrum is displayed and collected by the control system, and the control system controls the sample introduction system, the electrolyte discharge plasma generation system, the light path collection and filtering sorting system and the data processing system; the light path collecting and filtering sorting system is integrated on a cage type coaxial system and comprises a biconvex lens (2), a spatial filter (3), a front plano-convex lens, a narrow band filter and a rear plano-convex lens which are sequentially arranged along a light path, an emission spectrum emitted by electrolyte discharge plasma is collected by the biconvex lens positioned behind the plasma and is converged and imaged to the spatial filter (3) positioned behind the biconvex lens (2), the spatial filter (3) selects a main discharge light emitting area negative glow area of a metal element in the plasma, then the front plano-convex lens (4) positioned at f2 behind the spatial filter (3) converges a parallel light type spectrum of the negative glow area to the narrow band filter (5), and then the rear plano-convex lens (6) collects a selected metal element characteristic spectrum to a photosensitive surface of a photomultiplier positioned behind the rear plano-convex lens (6), the focal length of the biconvex lens is 3 cm-10 cm, f2 is the focal length of the front plano-convex lens, f2 is 3 cm-10 cm, the structure of the rear plano-convex lens is completely the same as that of the front plano-convex lens, and the biconvex lens and the plano-convex lens are both made of fused quartz materials; the narrow-band filter is a narrow-band-pass interference filter arranged on the electric filter wheel, the bandwidth is 5-30nm, and the light-passing central wavelength of the narrow-band filter is the emission wavelength of the metal element resonance line; the electric filter wheel is controllably connected with the control system so as to select the narrow-band filter corresponding to the measured metal element by controlling the electric filter wheel to filter stray light of other wave bands and select a metal element characteristic spectrum;
the detection method comprises the following steps of,
1) controlling the rotating speed of the two single-channel peristaltic pumps according to the pH value measured in the buffer cavity or the experimental calibration value of the non-acidified sample and the standard acid solution to adjust the mixing proportion of the sample to be measured and the standard acid solution, so that the pH value of the mixed solution is 1;
2) the mixed solution enters the conduit from the buffer cavity under the pressure of the single-channel peristaltic pump, and the buffer ball in the conduit further weakens the pulsation of the solution;
3) the control system controls a power supply formed by the lithium battery and the transformer to provide working voltage for the glow discharge atomizer and controls the electric injection valve to push downwards to compress the air bag, so that the flow rate of the solution is accelerated, and the solution is sprayed out of the glass capillary tube to be automatically ignited;
4) the control system controls the electric filter wheel to rotate so as to select the narrow-band filter corresponding to the measured metal element to filter out stray light of other wave bands and select a metal element characteristic spectrum;
5) the control system controls the three-dimensional adjusting device provided with the electrolyte discharge plasma excitation light source to realize the relative displacement of the electrolyte discharge plasma excitation light source and the light path collecting and filtering sorting system, so as to obtain the optimal signal of the metal element characteristic spectrum;
6) the photomultiplier in the data processing system collects the light transmitted by the light path collecting and filtering sorting system and converts the light into an electric signal, the electric signal is amplified by the current amplifier and then stored by the data collector, and the stored data is transmitted to a computer or other terminal equipment through the Bluetooth function and is analyzed and processed;
7) and repeating the steps 4, 5 and 6 until the data of the predetermined elements are measured.
The sampling system include two be used for respectively with the single channel peristaltic pump of acidized sample and the pump of standard acid solution into cushion chamber, one end with the cushion chamber intercommunication other end be connected to the pipe of the capillary glass pipe of electrolyte discharge plasma generation system, a plurality of quilt are held the pipe in buffer ball to and the supplementary generating device of plasma, the supplementary generating device of plasma including concatenating the gasbag between pipe and capillary glass pipe, set up and be in the gasbag on and with the controllable automatically controlled injection valve of connecting of control system, the rotational speed of single channel peristaltic pump respectively by control system controls.
The data processing system comprises a photomultiplier tube, a current amplifier and a data acquisition unit.
The buffer ball is made of glass or acid-proof materials, is placed in a horizontally placed guide pipe, and has the diameter of 3/4-4/3 of the diameter of the guide pipe.
The spatial filter is an optical slit with the length of 1-5 mm and the width of 50-100 mu m, and the upper and lower spatial positions of the spatial filter are adjustable.
The data acquisition unit in the analyzer also has WiFi and/or Bluetooth transmission functions, and stores the measurement result and transmits the data wirelessly.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a metal element analysis device which does not need to acidify a sample in advance, does not need carrier gas, has more stable discharge, simple and convenient operation, cheap equipment and smaller volume.
The detection method disclosed by the invention has the advantages of automatic detection, simplicity in operation and strong field adaptability, and greatly improves the field detection speed and precision.
Drawings
FIG. 1 is a schematic diagram of a portable elemental analyzer according to the present invention;
fig. 2 is a schematic diagram of a sample injection system.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1-2, a portable elemental analyzer of the present invention comprises: the system comprises a sample introduction system, an electrolyte discharge plasma generation system, a light path collection, filtering and sorting system, a data processing system and a control system; the electrolyte discharge plasma generating system comprises a power supply, a transformer 16 and a glow discharge atomizer 1 which are composed of a lithium battery and a transformer, a light path collecting and light filtering sorting system comprises a double convex lens 2, a space filter 3, plano-convex lenses 4 and 6 and a narrow band filter 5, the light path collecting and light filtering sorting system comprises a photomultiplier tube 7 and a current amplifier 8, and a transformer 17, a data processing system is a data collector 9 with a Bluetooth function, a control line is a controller, such as a computer 10, the sample injection system comprises a single-channel peristaltic pump 11, 12, 15, a sample buffer cavity 13, a sample injection buffer and a plasma auxiliary generating device 14, namely the single-channel peristaltic pump 11, 12, 15, the sample buffer cavity 13 and the sample injection system of the analyzer composed of the sample injection buffer and the plasma auxiliary generating device 14, the action of the single-channel peristaltic pumps 11, 12, 15 and the plasma auxiliary generating device in the sample introduction system is controlled by a control system, such as a computer 10.
The electrolyte discharge plasma generating system of the analyzer consists of an electrolyte glow discharge atomizer 1 and a transformer 16, an additional 12V lithium battery provides an input voltage, a working voltage is provided for the discharge system through the high voltage output by the transformer 16, and the output voltage of the transformer is controlled by a computer 10. That is, the entire elemental analyzer is powered by a 12V lithium battery. The lithium battery and the transformer provide working voltage for the glow discharge atomizer, and glow discharge is carried out on a sample entering from the sample introduction system to generate discharge plasma and emit element characteristic spectrum.
The light path collection and filtering sorting system composed of the biconvex lens 2, the spatial filter 3, the plano-convex lenses 4 and 6 and the narrow-band filter 5 collects element characteristic spectral lines, and the data processing system composed of the photomultiplier tube 7, the current amplifier 8 and the data collector 9 with the Bluetooth function converts the spectral signals collected by the optical system into electric signals and collects and stores the electric signals.
The data collector 9 and the computer 10 are a data storage, transmission and calculation analysis center of the whole analyzer, the computer controls the sample introduction system and the electrolyte discharge plasma generation system, and simultaneously controls the rotation of an electric filter wheel in the light path collection and filtering sorting system to select a narrow-band filter corresponding to a measured metal element and controls the output voltage of the transformer 17 to provide working voltage for the photomultiplier 7. And the data collected and stored by the data collector is transmitted to a computer or other terminal equipment through Bluetooth for data analysis and processing, so that the concentration of the metal elements in the sample to be detected is obtained.
The technical scheme adopts the electrolyte glow discharge which has low power consumption, does not need auxiliary gas and works under atmospheric pressure as an excitation source, has greater portability advantage than other plasma excitation sources such as ICP, MIP and DBD, and is particularly suitable for portable instruments. According to the portable instrument, the portable metal element analyzer for field survey can be realized, on-site rapid measurement equipment is provided for field survey of metal mineral sources such as potassium metal ores and lithium ores in salt lakes, and the portable instrument has great application value.
The element analyzer based on the scheme performs the following element measurement process:
the computer 10 controls the rotating speed of the single-channel peristaltic pumps 11, 12 in the sample introduction system, the sample to be measured and the standard acid solution are respectively pumped into the sample buffer cavity 13, the sample to be measured with the pH value of 1 is formed in the sample buffer cavity 13, the sample to be measured enters the electrolyte discharge atomizer 1 through the plasma auxiliary generation device 14, the computer 10 controls the power supply formed by the lithium battery and the transformer 16 to provide working voltage for the electrolyte discharge plasma generation system and controls the electric control injection valve 21 on the air bag 20 to push downwards, so that the sample to be measured is sprayed out from the upper end of the capillary glass tube to be automatically ignited, discharge plasma is generated, the sample to be measured does not need to be modulated in advance, the detection steps are simplified, and the convenience of field operation is further improved through automatic ignition.
The element characteristic spectral line emitted by the plasma enters a photomultiplier tube 7 through a light path collecting, filtering and sorting system consisting of a biconvex lens 2, a spatial filter 3, plano-convex lenses 4 and 6 and a narrow band filter 5 to be converted into an electric signal, the electric signal is amplified by a current amplifier 8 and then is collected and stored by a data collector 9, and the data is transmitted to a computer 10 or other terminal equipment through the Bluetooth function of the data collector to calculate the concentration of the metal element to be measured.
The sample introduction system in the element analyzer pumps a sample to be detected and an acid solution into a guide pipe by using two single-channel peristaltic pumps, the acid solution and the sample to be detected are converged in a sample buffer cavity by controlling the rotating speed of the two peristaltic pumps to form a standard sample solution with the pH value of 1, and the standard sample enters a glow discharge atomizer after being stabilized by the guide pipe provided with a buffer ball. The sample to be tested and the standard acid solution which are not acidified are introduced into the guide pipe by utilizing the sample introduction structure of the two single-channel peristaltic pumps, so that the sample does not need to be acidified in advance, and then flows more stably in the guide pipe through the guide pipe provided with the buffer ball, and finally enters the electrolyte discharge plasma generation system, so that the discharge is more stable.
Meanwhile, the element analyzer uses a plasma auxiliary generation device consisting of an air bag with an electric control injection valve, and realizes automatic ignition by controlling a valve through a computer.
A spatial filter is adopted in an optical path system of the element analyzer to extract a spectral signal of a spectral emission region of a metal element in discharge plasma, so that the signal-to-back ratio of signal receiving is improved, and the detection sensitivity of the analyzer is improved.
Because electrolyte glow discharge plasma emission spectrum is less, and the spectral line separation of different metallic elements is wider moreover, this elemental analyzer uses the narrowband optical filter to replace traditional monochromatic spectrometer for its structure is simpler, and the volume is littleer, and it is more convenient to operate, and the product price is cheaper.
The element analyzer collects optical signals by using a quartz lens, selects characteristic spectrum signals by using a narrow-band filter and a photomultiplier to convert the characteristic spectrum signals into electric signals, and performs data acquisition and processing by a subsequent data processing system, so that the volumes of an optical path system and the data processing system are smaller while the detection precision is ensured, the integration is convenient, and the cost of a detection device is reduced.
The internal structure of the element analyzer is as follows: the single-channel peristaltic pumps 11 and 12 in the sample feeding system are communicated with the buffer cavity 13 and are connected to a capillary glass tube of an electrolyte discharge plasma generating system through a guide tube 19 for placing a plurality of buffer balls 18, the plasma auxiliary generating device comprises an air bag 20 which is connected in series between the guide tube and the capillary glass tube, and an electric control injection valve 21 which is controllably connected with the control system is arranged on the air bag 20; the light path collecting, filtering and sorting system comprises a biconvex lens 2, a spatial filter 3, a front plano-convex lens 4, a narrow-band filter 5 and a rear plano-convex lens 6 which are arranged along a light path in sequence, the emission spectrum emitted by the plasma is collected by the biconvex lens 1 positioned in the plasma and is converged and imaged to the spatial filter 3 positioned behind the biconvex lens 1, if plasma is arranged at the front 2f1 of the biconvex lens 1, the space filter is arranged at the back 2f1 of the biconvex lens to form an image with the same size, the space filter selects a main negative glow area of a discharge area of the plasma, then a parallel light type spectrum of the negative glow area is converged to a narrow-band filter by the front plano-convex lens 4 arranged at the back f2 of the space filter 3, and then a selected metal element characteristic spectrum is collected and converged to a photosensitive surface of a photomultiplier 7 arranged behind the back plano-convex lens 6 by the back plano-convex lens 6. The focal length f1 of the biconvex lens is 3 cm-10 cm, the front plano-convex lens and the rear plano-convex lens are completely the same, the focal length f2 is 3 cm-10 cm, and the biconvex lens and the plano-convex lens are both made of fused quartz materials. The data processing system comprises a photomultiplier tube 7, a current amplifier 8 and a data collector 9 with WiFi and Bluetooth functions, the data collector is used for obtaining and storing the current intensity of each element, and the stored data are transmitted to a computer 10 or other terminal equipment through the Bluetooth function, so that the content of metal elements in the data can be quantitatively analyzed. Simultaneously, the waste liquid is discharged into a waste liquid pool through a single-channel peristaltic pump 15.
The sample to be tested and the acid solution which are not acidified enter the conduit through the single-channel peristaltic pump respectively, the acid solution and the sample to be tested are converged in the sample buffer cavity to form a standard sample solution with the pH value of 1 by controlling the rotating speed of the two peristaltic pumps, and the standard sample enters the glow discharge atomizer after being stabilized by the conduit provided with the buffer ball.
Preferably, the sample introduction system comprises two single-channel peristaltic pumps, a conduit provided with a buffer ball, a sample buffer cavity and a plasma auxiliary generation device, the plasma auxiliary generation device comprises an air bag with an automatic valve, and the actions of the peristaltic pumps and the plasma auxiliary generation device are controlled by a control system.
Preferably, the narrow-band filter is a narrow-band filter on an electric filter wheel, and the electric filter is controllably connected with the control system so as to control the filter wheel to be rotated through a computer to select the narrow-band filter corresponding to the measured metal element to filter stray light of other wave bands and select the metal element characteristic spectrum.
The width of the spatial filter is adjustable within the range of 50-100 mu m, and the spatial filter is used for spatially selecting a main discharge area of the discharged plasma after the plasma is imaged at the position of the spatial filter through the biconvex lens. Meanwhile, the electrolyte discharge plasma generating system is arranged on the support frame with adjustable height and front and back.
Preferably, the biconvex lens, the spatial filter, the front plano-convex lens, the narrow band filter, the rear plano-convex lens and the photomultiplier are fixedly integrated in a cage type coaxial system, so that all optical devices are coaxial and fixed in position, and adjustment is facilitated.
Preferably, the element analyzer further comprises a data collector with a bluetooth function, wherein the data collector is connected with the current amplifier, collects and stores data, and transmits the data to an external computer or other terminal equipment through the bluetooth function, so that the data analysis and processing are facilitated.
According to the invention, the electrolyte discharge plasma generating system and a set of three-dimensional adjustable supporting frame are arranged, the relative displacement between the plasma generating system and the light path collecting and filtering sorting system is adjusted through the control system, meanwhile, the width of the spatial filter is adjusted, and the signal intensity is observed, so that the optimal discharge position can be selected, a subsequent light path collecting device does not need to be adjusted, and the detection device is more convenient to operate. The space filter is adopted to perform space selection on the area of the plasma, the main discharge area of the plasma, namely the negative glow area of the plasma, is selected by adjusting and adjusting the relative displacement of the plasma generating system and the light path collecting and filtering sorting system, and effective light signals fully enter the photomultiplier, so that the signal-to-back ratio of signal receiving is improved, the detection sensitivity of the set of element analyzer is improved, and the space filter is matched with the detection device of the optical filter to ensure that the set of analyzer has smaller volume and cheaper equipment compared with the existing photoelectric detection device.
In summary, the light path collection and filtering sorting system of the element analyzer for field survey, which is disclosed by the invention, is different from the detection technology of a monochromatic spectrometer and a photomultiplier in the prior art, and the quartz lens, the spatial filter and the narrow-band filter are adopted to replace the monochromatic spectrometer, so that the whole detection system is cheaper in price and smaller in volume under the condition of higher spectral resolution, and the detection system is simpler and more convenient to operate by combining with a three-dimensional adjustable electrolyte discharge plasma generation system.
The specific detection method comprises the following steps of,
1) controlling the rotating speed of the two single-channel peristaltic pumps according to the pH value measured in the buffer cavity or the experimental calibration value of the non-acidified sample and the standard acid solution to adjust the mixing proportion of the sample to be measured and the standard acid solution, so that the pH value of the mixed solution is 1; namely, a pH meter which is in communication connection with a control system can be arranged in the buffer cavity, so that the rotation speed matching of the two single-channel peristaltic pumps can be automatically adjusted;
2) the mixed solution enters the conduit from the buffer cavity under the pressure of the single-channel peristaltic pump, and the buffer ball in the conduit further weakens the pulsation of the solution;
3) the control system controls a power supply formed by the lithium battery and the transformer to provide working voltage for the glow discharge atomizer and controls the electric injection valve to push downwards to compress the air bag, so that the flow rate of the solution is accelerated, and the solution is sprayed out of the glass capillary tube to be automatically ignited;
4) the control system controls the electric filter wheel to rotate so as to select the narrow-band filter corresponding to the measured metal element to filter out stray light of other wave bands and select a metal element characteristic spectrum;
5) the control system controls the three-dimensional adjusting device provided with the electrolyte discharge plasma excitation light source, so that the relative displacement between the electrolyte discharge plasma excitation light source and the light path collecting and filtering sorting system is realized, and the optimal signal of the metal element characteristic spectrum is obtained.
6) The photomultiplier in the data processing system collects the light transmitted by the light path collecting and filtering sorting system and converts the light into an electric signal, the electric signal is amplified by the current amplifier and then stored by the data collector, and the stored data is transmitted to a computer or other terminal equipment through the Bluetooth function and is analyzed and processed;
7) and repeating the steps 4, 5 and 6 until the data of the predetermined elements are measured.
The element analyzer realizes automatic adjustment of the pH value of the liquid, automatic ignition and continuous measurement, and can realize multi-element sequential measurement by automatically adjusting the optical filter, thereby effectively improving the measurement efficiency and reducing the use cost.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (3)

1. A detection method adopting a portable element analyzer for field survey is characterized in that the portable element analyzer for field survey comprises a sample introduction system, an electrolyte discharge plasma generation system, a light path collection, light filtering and sorting system, a data processing system and a control system; the sample introduction system introduces a sample into the electrolyte discharge plasma generation system to perform glow discharge to emit an element spectrum, the element spectrum is collected by the light path collection and filtering sorting system and transmitted to the data processing system, and finally the element spectrum is displayed and collected by the control system, and the control system controls the sample introduction system, the electrolyte discharge plasma generation system, the light path collection and filtering sorting system and the data processing system; the light path collecting and filtering sorting system is integrated on a cage type coaxial system and comprises a biconvex lens (2), a spatial filter (3), a front plano-convex lens, a narrow band filter and a rear plano-convex lens which are sequentially arranged along a light path, an emission spectrum emitted by electrolyte discharge plasma is collected by the biconvex lens positioned behind the plasma and is converged and imaged to the spatial filter (3) positioned behind the biconvex lens (2), the spatial filter (3) selects a main discharge light emitting area negative glow area of a metal element in the plasma, then the front plano-convex lens (4) positioned at f2 behind the spatial filter (3) converges a parallel light type spectrum of the negative glow area to the narrow band filter (5), and then the rear plano-convex lens (6) collects a selected metal element characteristic spectrum to a photosensitive surface of a photomultiplier positioned behind the rear plano-convex lens (6), the focal length of the double convex lens is 3 cm-10 cm, f2 is the focal length of the front planoconvex lens, f2 is 3 cm-10 cm, the structure of the rear planoconvex lens is completely the same as that of the front planoconvex lens, and the double convex lens and the planoconvex lens are both made of fused quartz materials; the narrow-band filter is a narrow-band-pass interference filter arranged on the electric filter wheel, the bandwidth is 5-30nm, and the light-passing central wavelength of the narrow-band filter is the emission wavelength of the metal element resonance line; the electric filter wheel is controllably connected with the control system so as to select the narrow-band filter corresponding to the measured metal element by controlling the electric filter wheel to filter stray light of other wave bands and select a metal element characteristic spectrum; the sample introduction system comprises two single-channel peristaltic pumps for respectively pumping an unacidified sample and a standard acid solution into a buffer cavity, a conduit with one end communicated with the buffer cavity and the other end connected to a capillary glass tube of an electrolyte discharge plasma generation system, a plurality of buffer balls accommodated in the conduit, and a plasma auxiliary generation device, wherein the plasma auxiliary generation device comprises an air bag connected between the conduit and the capillary glass tube in series, and an electric control injection valve arranged on the air bag and controllably connected with the control system, and the rotating speed of the single-channel peristaltic pumps is respectively controlled by the control system;
the detection method comprises the following steps of,
1) controlling the rotating speed of the two single-channel peristaltic pumps according to the pH value measured in the buffer cavity or the experimental calibration value of the non-acidified sample and the standard acid solution to adjust the mixing proportion of the sample to be measured and the standard acid solution, so that the pH value of the mixed solution is 1;
2) the mixed solution enters the conduit from the buffer cavity under the pressure of the single-channel peristaltic pump, and the buffer ball in the conduit further weakens the pulsation of the solution;
3) the control system controls a power supply formed by the lithium battery and the transformer to provide working voltage for the glow discharge atomizer and controls the electric injection valve to push downwards to compress the air bag, so that the flow rate of the solution is accelerated, and the solution is sprayed out of the glass capillary tube to be automatically ignited;
4) the control system controls the electric filter wheel to rotate so as to select the narrow-band filter corresponding to the measured metal element to filter out stray light of other wave bands and select a metal element characteristic spectrum;
5) the control system controls the three-dimensional adjusting device provided with the electrolyte discharge plasma excitation light source to realize the relative displacement of the electrolyte discharge plasma excitation light source and the light path collecting and filtering sorting system, so as to obtain the optimal signal of the metal element characteristic spectrum;
6) the photomultiplier in the data processing system collects the light transmitted by the light path collecting and filtering sorting system and converts the light into an electric signal, the electric signal is amplified by the current amplifier and then stored by the data collector, and the stored data is transmitted to a computer or other terminal equipment through the Bluetooth function and is analyzed and processed;
7) repeating the steps 4), 5) and 6) until the data of the predetermined element is measured.
2. The detection method of claim 1, wherein the data processing system comprises a photomultiplier tube, a current amplifier, and a data collector.
3. The detection method according to claim 1, wherein the spatial filter is an optical slit having a length of 1 to 5mm and a width of 50 to 100 μm, and the spatial filter has an adjustable upper and lower spatial position.
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