CN215339624U - Water body heavy metal detector with multi-range automatic switching function - Google Patents
Water body heavy metal detector with multi-range automatic switching function Download PDFInfo
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Abstract
The utility model relates to a water body heavy metal detector with a multi-range automatic switching function, which comprises a probe provided with a three-electrode sensor, and a host provided with a central processing module, a scanning voltage module, a potential compensation module, a signal acquisition processing module and a display module, wherein the scanning voltage module and the display module are respectively connected with the central processing module, the output end of the scanning voltage module is connected with a counter electrode of the three-electrode sensor through the potential compensation module, a reference electrode is connected with the feedback input end of the potential compensation module, and a working electrode is connected with the input end of the central processing module through the signal acquisition processing module. The signal acquisition processing module comprises N paths of I/V conversion circuits controlled to be switched on and switched off by the central processing module, the feedback resistance values of the N paths of I/V conversion circuits are different, and the N paths of I/V conversion circuits respectively correspond to N gear ranges. The utility model can carry out qualitative and quantitative analysis on various heavy metals in a water sample, has the function of multi-range automatic switching, and improves the detection accuracy.
Description
Technical Field
The utility model belongs to the technical field of water environment detection, and particularly relates to a water body heavy metal detector with a multi-range automatic switching function.
Background
With the development of industrialization in recent years, great economic benefits are brought, natural environment is damaged, and heavy metal pollution is becoming serious. Heavy metal means a density of greater than 4.5g/cm3The metal of (1) mainly contains 45 elements of Cu (copper), Pb (lead), Cd (cadmium), Hg (mercury), Zn (zinc), As (arsenic), Au (gold), Ag (silver), Cr (chromium), Ni (nickel) and the like, wherein the elements of Pb, Cd, Hg, As, Cr and the like which have the greatest harm to human bodies. Once entering the natural environment, these heavy metals are easily absorbed by animals and plants, accumulate in the body for a long time and are difficult to degrade, and when the accumulation exceeds the limit, the accumulation seriously affects the physiological activities of the animals and plants, and finally enters the human body along with the migration of food chains, thereby causing threats to human health, such as water guarantee disease (Hg pollution) and bone pain disease (Cd pollution) which are well known. Therefore, the heavy metal detection on the water body is very important.
At present, domestic and foreign water body heavy metal detection methods include atomic spectrometry, mass spectrometry, spectrophotometry and the like, although the method has great advantages in detection accuracy and is widely applied to the field of high-precision trace analysis, the method generally has the problems of high equipment price, high operation cost, large volume, complex operation, need of professional operation and the like, and various steps such as sampling, transferring, extracting, concentrating and the like are often needed for one-time detection, so that the rapid on-site detection and the rapid acquisition of on-site real-time data are difficult to realize. Although neotype biochemical analysis technique has greatly promoted in the convenient degree of use to there is high selectivity to specific ion, but the range of application has the restriction, generally can only single measurement a certain element, and easily receive external environment influence, can't satisfy the requirement that multiple heavy metal carries out the detection in the water, the detection range of equipment all is fixed in addition generally, detects time measuring to complicated water environment, can influence the accuracy nature of testing result.
Disclosure of Invention
In order to solve the technical problems, the utility model provides a water body heavy metal detector with a multi-range automatic switching function, which can simultaneously detect various heavy metal elements in a water body in the detection process, perform qualitative and quantitative analysis on various heavy metal ions in a water sample, has a wide application range, and meets the requirement of detecting various heavy metals in the water body.
The utility model also aims to provide a water body heavy metal detector with a multi-range automatic switching function, which has multiple ranges and can be automatically switched to the most appropriate corresponding range according to the result of pre-sampling, thereby achieving the best detection sensitivity, improving the accuracy of the detection result, solving the problems that different heavy metal ions in complex water environment and the wide variation range of response current at different concentration levels affect the detection sensitivity and the detection accuracy, and realizing the on-site real-time rapid detection of various heavy metals in the water body.
The technical problem of the utility model is mainly solved by the following technical scheme: the utility model comprises a probe and a host which are connected, wherein a three-electrode sensor is arranged in the probe, a control circuit is arranged in the host, the control circuit comprises a central processing module, a scanning voltage module, a potential compensation module, a signal acquisition processing module and a display module, the display module and the scanning voltage module are respectively connected with the central processing module, the output end of the scanning voltage module outputs a scanning voltage signal, the scanning voltage signal is a step scanning voltage signal with constant step and increment, and a constant-amplitude rectangular pulse is superposed on the stepped scanning voltage signal, the output end of the scanning voltage module is connected with the three-electrode sensor through the potential compensation module, the signal output end of the three-electrode sensor is connected with the input end of the signal acquisition processing module, and the output end of the signal acquisition processing module is connected with the input end of the central processing module.
When the device works, the probe is stretched into a water body to be detected, the central processing module accurately controls the scanning voltage module to output a scanning voltage signal required by detection, the waveform of the scanning voltage signal is obtained by superposing a rectangular pulse with constant amplitude on the step scanning voltage, and the step scanning voltage is increased in constant steps. The scanning voltage signal output by the scanning voltage module is applied to the three-electrode sensor through the potential compensation module, when the scanning voltage signal scans the oxidation potential of the metal element corresponding to the scanning voltage signal, if the heavy metal element exists in the water body, an oxidation reaction starts to occur, heavy metal is dissolved out from the surface of the electrode in an ionic state to the water body to generate a dissolved current signal, the generated weak current signal is accurately collected by the signal collection and processing module, and then the weak current signal is transmitted back to the central processing module for calculation and analysis through a series of processing, a current-voltage volt-ampere relation curve is established, so that the heavy metal component and the content in the water body to be detected are analyzed, and the detection result is output to the display module for display. According to the utility model, by applying the scanning voltage signal and utilizing the chemical characteristics of the heavy metal elements, namely different heavy metal elements have different characteristic dissolution potentials respectively, and the peak current value is in direct proportion to the concentration of the heavy metal ions within a certain range, the qualitative and quantitative analysis of various heavy metal ions in a water sample is realized, the application range is wide, and the requirement of detecting various heavy metals in a water body is met. The central processing module is used as a core controller of the instrument, and in the detection process, the central processing module generates a voltage modulation signal to control the work of the scanning voltage module, processes and analyzes the signal transmitted by the signal acquisition and processing module, and outputs the result to the display module. The potential compensation module is used for balancing potential change of the three-electrode sensor, and avoids that in the actual detection process, after current flows through a counter electrode in the three-electrode sensor along with the proceeding of electrochemical reaction, the counter electrode can be polarized to generate voltage drop, and the voltage drop can enable the voltage of a working electrode in the three-electrode sensor to gradually deviate from an initial value, so that a larger measurement error is caused. The potential compensation module is used for realizing the accurate control of the potential of the electrode, so that the voltage between the working electrode and the reference electrode in the three-electrode sensor is constant, and a strong stripping current signal is generated in a test loop formed by the working electrode and the counter electrode. The scanning voltage signal output by the scanning voltage module is a step scanning voltage formed in a constant step increasing mode, the precision of the scanning voltage signal can be improved by controlling the step voltage, and the detection precision is further improved.
Preferably, the scan voltage module comprises a digital-to-analog conversion unit, an operational amplifier unit and a reference voltage unit, wherein the output end of the central processing module is connected with the input end of the digital-to-analog conversion unit, the output end of the digital-to-analog conversion unit is connected with the input end of the operational amplifier unit, the output end of the operational amplifier unit is connected with the potential compensation module, and the reference voltage unit is connected with the digital-to-analog conversion unit. The operational amplifier unit and the digital-to-analog conversion unit form a scanning voltage circuit, and the reference voltage unit provides stable and accurate reference voltage for the scanning voltage circuit. The scanning voltage module generates a scanning voltage signal required by detection under the control of the central processing module, the scanning voltage signal is a step scanning voltage formed in a constant step increasing mode, the precision of the scanning voltage signal can be improved by controlling the step voltage, and the detection precision of heavy metal ions is further improved.
Preferably, the three-electrode sensor comprises a working electrode, a counter electrode and a reference electrode, the counter electrode is connected with the output end of the potential compensation module, the reference electrode is connected with the feedback input end of the potential compensation module, the working electrode is the signal output end of the three-electrode sensor, and the working electrode is connected with the input end of the signal acquisition processing module. The three-electrode sensor adopts a three-electrode system, a reference electrode is introduced on the basis of a traditional two-electrode system consisting of an electrolytic cell, a working electrode and a counter electrode, no current flows through the reference electrode, and only one reference object is provided for the working electrode to maintain the potential on the working electrode constant. The counter electrode is responsible for conducting current, and forms a current measurement loop with the working electrode, and the voltage between the reference electrode and the working electrode is controlled by the potential compensation module. The potential compensation module is used for realizing the accurate control of the potential of the electrode, so that the voltage between the working electrode and the reference electrode in the three-electrode sensor is constant, and a strong stripping current signal is generated in a test loop formed by the working electrode and the counter electrode.
Preferably, the working electrode, the counter electrode and the reference electrode are all electrodes which take a quartz substrate as a substrate and adopt a bismuth ion modification technology, the working electrode is made of a carbon nano material, the counter electrode is made of a carbon material, and the reference electrode is made of a silver-silver chloride material. The three-electrode sensor adopts a bismuth ion modification technology, improves the sensitivity and stability of the electrode, and adopts a microelectrode, so that the volume is small and the repeatability is good.
Preferably, the signal acquisition and processing module comprises N paths of I/V conversion circuits controlled to be switched on and switched off by the central processing module, the resistance values of feedback resistors of the N paths of I/V conversion circuits are different, and the N paths of I/V conversion circuits respectively correspond to the measuring ranges of N gears. Wherein N is more than or equal to 3. The on-off of the I/V conversion circuit is controlled by the central processing module, the central processing module selects which gear range to detect, and only the corresponding path of I/V conversion circuit is controlled to be switched on, so that the multi-range automatic switching is realized.
Preferably, the I/V conversion circuit has four paths, each path of I/V conversion circuit is provided with an analog switch, the signal acquisition processing module further comprises a low-pass filter circuit, a voltage amplification circuit and an a/D conversion circuit, the signal output end of the three-electrode sensor is connected with the input end of the four paths of I/V conversion circuit, the output end of the four paths of I/V conversion circuit is connected with the input end of the low-pass filter circuit, the output end of the low-pass filter circuit is connected with the input end of the a/D conversion circuit through the voltage amplification circuit, the output end of the a/D conversion circuit is connected with the input end of the central processing module, and the control ends of the analog switches of the four paths of I/V conversion circuit are respectively connected with the control signal output end of the central processing module. The weak current signal collected by the signal collecting and processing module is converted into a voltage signal with a certain amplitude through the I/V conversion circuit, then the signal is filtered by the low-pass filter circuit, so that the situation that the effective signal is amplified and the noise signal is amplified to cause the effective signal to be submerged in noise is avoided, the amplitude of the filtered signal is about dozens of millivolts, then the filtered signal is adjusted to a proper range through the voltage amplification circuit, finally the filtered signal is subjected to analog-to-digital conversion through the A/D conversion circuit and then is transmitted back to the central processing module for calculation, a current-voltage volt-ampere relation curve is established, and then the heavy metal components and the content of a sample to be detected are analyzed. The on-off of an analog switch of the I/V conversion circuit is controlled by the central processing module, and the central processing module judges the current range according to the result of pre-sampling. The method comprises the steps of firstly carrying out pre-sampling before formal sampling in each pulse period of a scanning voltage signal, when a pre-sampling current falls in the range of a certain gear, controlling the I/V conversion circuit corresponding to the gear range to be communicated by a central processing module, namely selecting the gear range, and then carrying out formal sampling detection, so that automatic switching of multiple ranges in the detection process is realized, and formal detection according to the optimal gear range is ensured, thereby improving the detection sensitivity and accuracy, solving the problems that detection sensitivity and detection accuracy are influenced by different heavy metal ions in a complex water environment and the wide variation range of the response current at different concentration levels, and realizing the field real-time rapid detection of multiple heavy metals in a water body.
The utility model has the beneficial effects that: by applying a scanning voltage signal, the chemical characteristics of the heavy metal elements are utilized, namely different heavy metal elements have different characteristic stripping potentials respectively, and the peak current value is in direct proportion to the concentration of the heavy metal ions in a certain range, so that qualitative and quantitative analysis of various heavy metal ions in a water sample is realized, the application range is wide, and the requirement of detecting various heavy metals in a water body is met. The signal acquisition processing module with the multi-path I/V conversion circuit is adopted to realize the automatic switching of multi-gear range, thereby achieving the best detection sensitivity, improving the accuracy of detection results and solving the problems that the detection sensitivity and the detection accuracy are influenced by different heavy metal ions in the complex water environment and the wide variation range of the response current under different concentration levels. The utility model has the advantages of small structure, convenient carrying, small sampling amount, convenient operation, high stability and high detection speed, and meets the requirement of on-site real-time and rapid detection of various heavy metals in a water body.
Drawings
Fig. 1 is a block diagram of a schematic circuit connection structure of a control circuit in a host according to the present invention.
Fig. 2 is a block diagram of a circuit schematic connection structure of the scan voltage module according to the present invention.
Fig. 3 is a block diagram of a circuit principle connection structure of the signal acquisition processing module according to the present invention.
Fig. 4 is a front view of the probe of the present invention.
Fig. 5 is a flow chart of the multi-range automatic switching process in the present invention.
In the figure, 1 is a central processing module, 2 is a scanning voltage module, 3 is a potential compensation module, 4 is a signal acquisition processing module, 5 is a display module, 6 is a digital-to-analog conversion unit, 7 is an operational amplifier unit, 8 is a reference voltage unit, 9 is a low-pass filter circuit, 10 is a voltage amplification circuit, 11 is an A/D conversion circuit, 12 is an I/V conversion circuit, 13 is an analog switch, 14 is a three-electrode sensor, 15 is a counter electrode, 16 is a reference electrode, 17 is a working electrode, 18 is a protective shell, and 19 is a base.
Detailed Description
The technical scheme of the utility model is further specifically described by the following embodiments and the accompanying drawings.
Example (b): the water body heavy metal detector with the multi-range automatic switching function comprises a probe and a host, wherein a three-electrode sensor 14 is installed in the probe, and a control circuit is installed in the host.
As shown in fig. 4, the probe includes a protective case 18 and a base 19. The protective housing is a cylinder, adopts transparent ya keli material, and the protective housing diameter is 60mm, is high for 60 mm. The base adopts the stainless steel, and inside adopts the polytetrafluoroethylene material, and the centre is opened has a length to be 30mm, wide for 0.5 mm's recess, and three electrode sensor of recess department installation. The three-electrode sensor is a microelectrode, the three-electrode sensor 14 comprises a working electrode 17, a counter electrode 15 and a reference electrode 16, the working electrode, the counter electrode and the reference electrode use a quartz substrate as a substrate, a bismuth ion modification technology is adopted, the working electrode is made of carbon nano materials, the counter electrode is made of carbon materials, the reference electrode is made of silver-silver chloride materials, and the size of the three-electrode sensor is 50.0 multiplied by 30.0 multiplied by 0.5 mm.
As shown in fig. 1, 2 and 3, the control circuit includes a central processing module 1, a scan voltage module 2, a potential compensation module 3, a signal acquisition processing module 4 and a display module 5, the scan voltage module includes a digital-to-analog conversion unit 6, an operational amplifier unit 7 and a reference voltage unit 8, the signal acquisition processing module includes a low-pass filter circuit 9, a voltage amplifier circuit 10, an a/D conversion circuit 11 and a four-way I/V conversion circuit 12, the four-way I/V conversion circuit has an analog switch 13, the feedback resistors of the four-way I/V conversion circuit are different in resistance, the four-way I/V conversion circuit respectively corresponds to the ranges of four gears, the four gear ranges are respectively 0.1 muA-20 muA, 15 muA-65 muA, 50 muA-250 muA and 200 muA-1000 muA. The display module is connected with the central processing module, the output end of the central processing module is connected with the input end of the digital-to-analog conversion unit, the output end of the digital-to-analog conversion unit is connected with the input end of the operational amplifier unit, the output end of the operational amplifier unit is connected with the input end of the potential compensation module, the reference voltage unit is connected with the digital-to-analog conversion unit, the output end of the operational amplifier unit outputs a scanning voltage signal, the scanning voltage signal is a step scanning voltage signal with constant step and increment, a rectangular pulse with constant amplitude is superposed on the step scanning voltage signal, the output end of the potential compensation module is connected with a counter electrode, a reference electrode is connected with the feedback input end of the potential compensation module, a working electrode is the signal output end of the three-electrode sensor, the working electrode is connected with the input end of the four-way I/V conversion circuit, and the output end of the four-way I/V conversion circuit is connected with the input end of the low-pass filter circuit, the output end of the low-pass filter circuit is connected with the input end of the A/D conversion circuit through the voltage amplification circuit, the output end of the A/D conversion circuit is connected with the input end of the central processing module, and the control ends of the analog switches of the four paths of I/V conversion circuits are respectively connected with the control signal output end of the central processing module.
In this embodiment, the central processing module is an enhanced 32-bit microprocessor with an ARM Cortex-M3 kernel architecture, which is produced by semiconductor corporation and has high data processing capability, low power consumption, and a working temperature range of-40 ℃ to 105 ℃, and meets the requirements of outdoor field detection. In order to ensure the accuracy of the scanning voltage signal in the detection process, the inherent error of the digital-to-analog conversion unit and the performance of the operational amplifier unit and the accuracy of the reference voltage unit are required. In order to enable the precision of the scanning voltage signal to meet the detection requirement, the digital-to-analog conversion unit adopts a digital-to-analog conversion chip DAC8831 which is high in precision and low in power consumption and outputs bipolar voltage, has a very high conversion rate (the establishment time is 1 mu s), has an inherent error of not more than +/-1 LSB and low power consumption of 15 mu W, and is matched with a central processing module to generate the scanning voltage signal required by detection; the operational amplifier unit adopts a high-precision operational amplifier OPA277 with low offset voltage and low temperature drift; the reference voltage unit adopts a REF3220 precision reference source chip produced by TI company, and can provide stable and precise reference voltage for the scanning voltage circuit. In the embodiment, a 12V lithium battery is used as an external power supply of the whole instrument, the 12V lithium battery provides stable working voltage for the whole instrument through a power module, and the power module has over-temperature and over-current protection functions.
The working process is as follows: the probe is extended into a water body to be detected, the central processing module controls the scanning voltage module to enable the output end of the scanning voltage module to output a scanning voltage signal, the scanning voltage signal is a step scanning voltage signal with constant step increasing, a rectangular pulse with constant amplitude is superposed on the step scanning voltage signal, the scanning voltage signal generated by the scanning voltage module is applied to a counter electrode of the three-electrode sensor by the potential compensation module, when the scanning voltage signal scans the oxidation potential of the heavy metal element corresponding to the scanning voltage signal, if the heavy metal element exists in the water body, an oxidation reaction starts to occur, the heavy metal is dissolved out from the surface of the electrode into the water body in an ionic state, the generated dissolved current signal is transmitted to the signal acquisition processing module through a working electrode of the three-electrode sensor, and the signal acquisition processing module converts the current signal into a voltage signal, and the water quality testing device is conveyed to a central processing module for calculation and analysis, and is switched to the optimal gear range for detection through a multi-range automatic switching function, so that the components and the content of various heavy metals in the water body to be detected are finally obtained, and the detection result is conveyed to a display screen for display.
In the multi-range automatic switching process, a 25% margin is also set, as shown in fig. 5: the method comprises the steps of firstly carrying out pre-sampling before formal sampling, firstly controlling the I/V conversion circuit corresponding to the range of the maximum gear to be communicated by the central processing module, judging the current range according to the result of the pre-sampling, selecting the range of the lower gear if the pre-sampling current value is less than 25% of the upper limit value of the range of the gear, namely controlling the I/V conversion circuit corresponding to the range of the lower gear to be communicated by the central processing module, and carrying out formal sampling detection until the pre-sampling current value is not less than 25% of the upper limit value of the range of the selected gear, so that the purpose of automatically switching to the optimal gear range according to the content of heavy metal in the water body is achieved, and multi-range automatic switching is realized.
Claims (6)
1.A water body heavy metal detector with a multi-range automatic switching function is characterized by comprising a probe and a host which are connected, wherein a three-electrode sensor is arranged in the probe, a control circuit is arranged in the host and comprises a central processing module, a scanning voltage module, a potential compensation module, a signal acquisition processing module and a display module, the display module and the scanning voltage module are respectively connected with the central processing module, the output end of the scanning voltage module outputs a scanning voltage signal which is a step scanning voltage signal with constant step increment, a rectangular pulse with constant amplitude is superposed on the step scanning voltage signal, the output end of the scanning voltage module is connected with the three-electrode sensor through the potential compensation module, the signal output end of the three-electrode sensor is connected with the input end of the signal acquisition processing module, the output end of the signal acquisition processing module is connected with the input end of the central processing module.
2. The water body heavy metal detector with the multi-range automatic switching function according to claim 1, wherein the scanning voltage module comprises a digital-to-analog conversion unit, an operational amplifier unit and a reference voltage unit, an output end of the central processing module is connected with an input end of the digital-to-analog conversion unit, an output end of the digital-to-analog conversion unit is connected with an input end of the operational amplifier unit, an output end of the operational amplifier unit is connected with the potential compensation module, and the reference voltage unit is connected with the digital-to-analog conversion unit.
3. The water body heavy metal detector with the multi-range automatic switching function according to claim 1, characterized in that the three-electrode sensor comprises a working electrode, a counter electrode and a reference electrode, the counter electrode is connected with an output end of the potential compensation module, the reference electrode is connected with a feedback input end of the potential compensation module, the working electrode is a signal output end of the three-electrode sensor, and the working electrode is connected with an input end of the signal acquisition and processing module.
4. The water body heavy metal detector with the multi-range automatic switching function according to claim 3, characterized in that the working electrode, the counter electrode and the reference electrode are all electrodes which take a quartz substrate as a substrate and adopt a bismuth ion modification technology, the working electrode is made of a carbon nano material, the counter electrode is made of a carbon material, and the reference electrode is made of a silver-silver chloride material.
5. The water body heavy metal detector with the multi-range automatic switching function according to claim 1, 2 or 3, characterized in that the signal acquisition and processing module comprises N paths of I/V conversion circuits controlled to be switched on and off by the central processing module, the feedback resistance values of the N paths of I/V conversion circuits are different, and the N paths of I/V conversion circuits respectively correspond to the ranges of N gears.
6. The water body heavy metal detector with the multi-range automatic switching function according to claim 5, it is characterized in that the I/V conversion circuit has four paths, each path of I/V conversion circuit is provided with an analog switch, the signal acquisition and processing module further comprises a low-pass filter circuit, a voltage amplification circuit and an A/D conversion circuit, wherein the signal output end of the three-electrode sensor is connected with the input end of the four paths of I/V conversion circuits, the output ends of the four paths of I/V conversion circuits are connected with the input end of the low-pass filter circuit, the output end of the low-pass filter circuit is connected with the input end of the A/D conversion circuit through the voltage amplification circuit, the output end of the A/D conversion circuit is connected with the input end of the central processing module, and the control ends of analog switches of the four paths of I/V conversion circuits are respectively connected with the control signal output end of the central processing module.
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