Heavy metal ion real-time automatic detection device and method based on unmanned ship

Abstract

The invention discloses a heavy metal ion real-time automatic detection device and method based on an unmanned ship. The device is composed of a ship body, a power system, a water sample collection module, a communication module, a monitoring control unit and an integrated detection system, the integrated system comprises a pretreatment cabin, a reaction cabin, a multi-cuvette rotating device and an ultraviolet and visible spectrophotometer, and continuous water sample treatment is achieved through an automatic dosing and liquid separation mechanism. The method comprises the following eight steps: collecting a water sample through a micro water pump, monitoring environmental parameters in real time, dynamically calculating the reagent addition amount, sequentially carrying out pH adjustment, chromogenic reaction and absorbance determination through a spectrophotometer, and calculating the heavy metal ion concentration in real time in combination with a standard curve. A traditional chemical detection method is creatively combined with an unmanned ship platform, in-situ real-time detection of heavy metal ions is achieved through full-process automation, and the method is particularly suitable for high-pollution, narrow water areas and other scenes where manual sampling is difficult.

Description

Technical Field

[0001] The embodiments of the present application relate to the field of marine or river water hydrological basic measurement and environmental inspection and testing services, and particularly to a real-time automatic detection device and method for heavy metal ions based on an unmanned ship. Background Art

[0002] With the development of chemical technology, there are a large number of advanced water quality detection devices on the market. These include, but are not limited to, real-time detection devices for basic data such as pH value, oxygen content, and nitrogen-oxygen ratio. However, the detection devices that can be carried by modern unmanned ships are relatively simple, and the data that can be measured is relatively basic, making it impossible to apply to more specific detection environments.

[0003] In response to the call of national policies such as green chemistry, the detection of pollutants in the watershed near chemical plants has become increasingly important. From the perspective of industrial geography and economic layout, the phenomenon of chemical plants clustering along the coast and rivers is the result of the synergistic effect of multiple factors. First, chemical production has the characteristic of high water consumption (10 - 50 m 3 of water consumption per ton of product), and using the water resources in the surrounding watershed as a cooling medium and process water source can reduce the water intake cost by 30 - 45%; second, each chemical plant relies on river and sea ports to achieve large-scale maritime transportation of bulk raw materials such as crude oil. However, some companies, in pursuit of production profits, discharge production waste without complete and professional treatment, resulting in serious heavy metal ion / organic matter pollution problems in the watershed near the factory. Among them, there are heavy metal ions such as the widely used catalyst Cr(Ⅵ) that are difficult to remove.

[0004] Cr has strong catalytic performance and has been widely used in various chemical productions. At the same time, chromium catalysts have serious pollution and are easy to lose. They are likely to cause serious damage to water bodies in the natural environment. Hexavalent chromium in water mainly invades the human body through the digestive tract, skin, and mucous membranes, causing irreversible diseases such as skin allergies, digestive system disorders, kidney function damage, and nervous system damage.

[0005] At present, the water quality detection of polluted watersheds mainly relies on manual sampling. Even when wearing protective equipment, various heavy metal ions still pose a great threat to human health. At the same time, the manual detection method has a too long detection cycle, low sample transfer efficiency, and it is difficult to guarantee the timeliness of obtaining experimental data, which has a significant blocking effect on the overall research process. Therefore, this technology uses an unmanned ship to carry a new type of professional detection equipment to save manpower while ensuring the efficient progress of detection. Summary of the Invention

[0006] The embodiment of the present application provides a real-time automatic detection device and method for heavy metal ions based on an unmanned ship, which cooperate with the hull GPS positioning system to achieve tasks such as sampling point positioning, water sample collection, and water sample storage. While improving the efficiency of water sample collection and saving labor costs, it meets the use requirements in difficult-to-access environments such as highly polluted and narrow river channels.

[0007] In the first aspect of the embodiment of the present application, a real-time automatic detection device for heavy metal ions based on an unmanned ship is provided, including a hull, a power system carried on the hull, a water sample collection module, a communication module and a data transmission module, a monitoring and control unit, and an integrated detection system; wherein, the integrated detection system includes: a pretreatment chamber for holding the collected water sample, and each dosing chamber selectively adds reagents to the pretreatment chamber and precisely controls the addition amount of the reagents through the volume control system; the pretreatment chamber pre-treats the water sample after adding the reagents; a reaction chamber for holding the water sample pretreated by the pretreatment chamber and where a chemical reaction occurs therein; a plurality of colorimetric cuvettes for receiving the water sample to be detected in the reaction chamber; and an ultraviolet-visible spectrophotometer for performing spectral analysis on the water sample in the colorimetric cuvette to determine the concentration of heavy metal ions.

[0008] A plurality of waste liquid bottles for collecting the waste liquid in the reaction chamber; a waste liquid bottle axle for driving the position switching of the plurality of waste liquid bottles to achieve the sub-packaging and storage of the waste liquid; a colorimetric cuvette axle for driving the position switching of the plurality of colorimetric cuvettes to achieve receiving different water samples to be detected and sequentially detecting different water samples in the plurality of colorimetric cuvettes.

[0009] On the other hand, the present application also provides a real-time automatic detection method for heavy metal ions based on an unmanned ship. The unmanned ship moves to the target water area, and the automatic detection method includes the following steps:

[0010] S1: Water sample collection; Using a micro water pump and a sampling tube, the water sample to be tested is extracted at a preset depth and transported to the pretreatment chamber; S2: Acquisition of environmental parameters and reagent calculation. The integrated probe is used to obtain the environmental data of the water sample in the pretreatment chamber in real time, and the central controller dynamically calculates the type and dosage of the reagent to be added according to the detected environmental data; S3: Water sample pretreatment. Add a pH adjustment reagent to the water sample until it reaches the preset value, and then add the corresponding amount of auxiliary reagent and chromogenic reagent; S4: Chromogenic reaction. Transfer the pretreated sample solution to the reaction chamber and let it stand for a preset time to fully react; S5: Sample aliquoting. Inject the reacted sample solution into the corresponding standard colorimetric cuvette to form a set of detection units; S6: Spectral analysis. Use an ultraviolet-visible spectrophotometer to measure the absorbance of the solution in the colorimetric cuvette at a preset wavelength; S7: Data processing and calculation. Calculate the heavy metal ion concentration directly according to the standard curve equation preset by the absorbance and mass, and convert the final detection value according to the preset concentration model; S8: Data transmission and control. The final detection value is transmitted back in real time through the communication module, and the colorimetric cuvette wheel shaft is controlled to switch to the next set of detection units.

[0011] Analysis shows that the present invention discloses a real-time automatic detection device for heavy metal ions of an unmanned ship, which can obtain the concentration data of heavy metals (such as hexavalent chromium ions) without the detection personnel directly contacting the water body to be detected. Under the condition of ensuring the personal safety of the detection personnel, the pollution degree of the water area to be detected can be preliminarily judged. The process is simplified, the detection process of heavy metals is accelerated, and the real-time detection of the concentration of heavy metal ions is realized. There is no need for laboratory detection with low timeliness, complex process and long cycle. This application applies the traditional detection method to the new scenario of an unmanned ship, and at the same time enables the detection personnel to obtain the target water sample and data in the remote operation scenario, so as to realize a new way for the remote and rapid detection of hexavalent chromium ions. The system is equipped with a waste liquid dispensing mechanism and a wheel shaft switching device, which significantly improves the detection efficiency while ensuring the safety of the detection personnel. Compared with laboratory detection, the present invention has the advantages of strong instantaneity and low operation risk, and provides a new solution for the monitoring of water body heavy metal pollution. Brief Description of the Drawings

[0012] The specification drawings forming a part of this application are used to provide a further understanding of this application. The schematic embodiments of this application and their descriptions are used to explain this application and do not constitute an improper limitation to this application. Among them:

[0013] Figure 1 It is a schematic diagram of the structures of various components of the unmanned ship in the embodiment of this application;

[0014] Figure 2 It is a schematic diagram of the determination of Cr(Ⅵ) by the integrated detection system in the embodiment of this application;

[0015] Figure 3 It is a schematic diagram of the hull structure material of the unmanned ship;

[0016] Description of the reference numerals in the drawings:

[0017] 1 - Integrated sensor; 2 - Integrated probe; 3 - Sampling tube; 4 - Pretreatment chamber; 41 - Stirrer; 5 - Integrated probe; 6 - Drug administration chamber; 7 - Reaction chamber; 8 - Waste liquid bottle; 9 - Colorimetric cell; 10 - Waste liquid bottle axle; 11 - Colorimetric cell axle; 110 - Position to be measured by the photometer; 12 - Ultraviolet-visible spectrophotometer; 13 - Micro water pump; 14 - Communication module and data transmission module; 15 - Lithium-ion battery system.

[0018] 20 - Housing; 30 - Insulation layer; 40 - Coating. Specific embodiments

[0019] The present application will be described in detail below with reference to the drawings and in conjunction with embodiments. Each example is provided by way of explanation of the present application rather than a limitation of the present application. In fact, those skilled in the art will appreciate that modifications and variations can be made to the present application without departing from the scope or spirit of the present application. For example, features shown or described as part of one embodiment can be used in another embodiment to yield yet another embodiment. Accordingly, it is intended that the present application cover such modifications and variations that fall within the scope of the appended claims and their equivalents.

[0020] In the description of the present application, the orientation or positional relationship indicated by the terms "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present application rather than requiring the present application to be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation of the present application. The terms "connected", "connected to", and "disposed" used in the present application should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection; it can be directly connected or indirectly connected through an intermediate component; it can be a wired connection, a radio connection, or a wireless communication signal connection. Those of ordinary skill in the art can understand the specific meanings of the above terms according to specific circumstances.

[0021] One or more examples of the present application are shown in the accompanying drawings. The detailed description uses numerical and alphabetical labels to refer to features in the drawings. Similar or like labels in the drawings and the description have been used to refer to similar or like parts of the present application. As used herein, terms such as "first", "second", and "third" can be used interchangeably to distinguish one component from another and are not intended to indicate the position or importance of individual components.

[0022] Embodiment 1

[0023] As Figures 1 to 3As shown, according to an embodiment of the present application, a real-time automatic heavy metal ion detection device based on an unmanned ship is provided, aiming to achieve efficient and stable water quality monitoring in complex and diverse working scenarios through an unmanned ship constructed of composite materials. To cope with the diversity and complexity of the working scenarios of the unmanned ship, the hull is constructed of composite materials. Specifically, in the embodiment of the present application, the hull structure adopts composite materials such as carbon fiber and glass fiber, which have the characteristics of light weight, high strength, and corrosion resistance, such as Figure 3 As shown, the hull includes an aluminum alloy shell 20, the outer surface of which is coated with a corrosion-resistant and electromagnetic interference-resistant coating 40, and its interior is wrapped with a carbon fiber and glass fiber filling layer to form a composite material structure of an insulating layer 30. In terms of the hull shape design of the hull structure, a flat-bottom hull design is adopted to ensure efficient operation in shallow water areas or complex waters. The hull structure is internally equipped with a power system, a central controller, a water sample collection module, a communication module, a data transmission module, a monitoring and control unit, and an integrated detection system mounted on the hull structure.

[0024] The power system is powered by a lithium-ion battery system 15 to ensure environmentally friendly operation over medium and short distances. The lithium-ion battery system 15 has the characteristics of high energy density and long life, and is suitable for the long-term operation requirements of the unmanned ship. The power system also includes a propulsion device, and a tail propeller is installed at the tail of the unmanned ship and is driven by an electric motor to achieve stable operation and accurate positioning and stopping of the unmanned ship. The design of the propeller takes into account efficiency and low-noise requirements to ensure smooth operation under various water conditions.

[0025] The water sample collection module includes a micro water pump 13 and a sampling tube 3, and collects water samples according to a preset depth. The sampling tube 3 can extend to a predetermined depth, and the water sample to be measured is pumped into the pretreatment chamber 4 through the micro water pump 13. The design of the sampling tube 3 takes into account corrosion resistance and flexibility to adapt to different water depths and water quality conditions.

[0026] In some embodiments, the integrated detection system includes five cylindrical reagent delivery chambers 6, a pretreatment chamber 4, a reaction chamber 7, a plurality of colorimetric cuvettes 9, and an ultraviolet-visible spectrophotometer 12. Among them, the five reagent delivery chambers 6 for loading reagents are all lined with fiberglass to prevent the reagents from corroding the containers. The pH adjustment reagents are respectively loaded with nitric acid (analytical pure) and sodium hydroxide solution (0.1 mol / L); the auxiliary reagents are respectively loaded with sulfuric acid (analytical pure), phosphoric acid (analytical pure), and a colorimetric reagent (0.25 g diphenylcarbazide: 100 mL acetone). Each reagent delivery chamber 6 is provided with a piston at the upper end, and the injection volume is calculated by measuring the piston displacement to achieve precise volume control.

[0027] In some embodiments, the pretreatment chamber 4 uses fiberglass as the inner lining to prevent the corrosion of the reagent on the chamber body. It is connected to the dosing chamber 6 through capillary tubes to ensure that the reagent can be accurately added to the pretreatment chamber 4. A stirrer 41 is provided inside the pretreatment chamber 4 to uniformly mix the reagent added to the pretreatment chamber 4 with the solution, thereby pretreating the water sample.

[0028] In some embodiments, the reaction chamber 7 uses fiberglass as the inner lining to prevent the corrosion of the reaction chamber 7 body by chemical reactions. The reaction chamber 7 is a place for the water sample to react. The reaction chamber 7 is connected to the waste liquid bottle 8 and the colorimetric cuvette 9 through gates to ensure that the water sample after the reaction can be smoothly transferred to the next processing step; each reagent of the pH adjustment reagent, auxiliary reagent, and colorimetric reagent in the dosing chamber 6 is connected to the pretreatment chamber 4 through pipelines; in some embodiments, each colorimetric reagent in the dosing chamber 6 is directly connected to the reaction chamber 7 through pipelines.

[0029] In some embodiments, the waste liquid axle 10 has multiple slots for placing the waste liquid bottles 8. By rotating the waste liquid axle 10, the waste liquid bottle 8 for receiving the waste liquid is changed to ensure that the waste liquid can be collected orderly.

[0030] In some embodiments, the colorimetric cuvette axle 11 has multiple slots for rotating the colorimetric cuvettes 9. By rotating the colorimetric cuvette axle 11, the colorimetric cuvette 9 for receiving the water sample is changed. The colorimetric cuvettes 9 are all 1-cm colorimetric cuvettes to ensure the consistency of spectral analysis.

[0031] In some embodiments, the ultraviolet-visible spectrophotometer 12 performs spectral analysis on the water sample in the reaction chamber 7. It is equipped with a dedicated detection channel with a wavelength of 540 nm and supporting optical components, suitable for the detection of hexavalent chromium ions. It also includes a liftable optical path isolation plate to form a closed optical channel during measurement to avoid external interference; the rotary colorimetric cuvette positioning mechanism is mechanically coupled with the colorimetric cuvette axle 11 system to ensure the accurate alignment of the position of the photometric measurement position 110 of the colorimetric cuvette 9 during each measurement, and a detailed water quality report is generated through the central controller.

[0032] In some embodiments, the real-time automatic detection device for heavy metal ions based on an unmanned ship further includes a monitoring and control unit, which includes an integrated probe 2, an integrated probe 5, and an integrated sensor 1.

[0033] Among them, the integrated probe 2 is usually used to directly measure the physical and chemical parameters in the water body.

[0034] The integrated probe 5 includes but is not limited to the following: First, a pH probe, which is applied to water environment monitoring to measure the acidity and alkalinity (pH value) of water, one of the important parameters for evaluating water quality; Second, a temperature probe, which measures the temperature of water because many chemical reactions and biological processes are closely related to temperature; Third, a conductivity probe, which measures the conductivity of water, indirectly reflects the ion concentration in water, and can also evaluate the content of dissolved salts and other ionic substances in water.

[0035] The integrated probe 2 includes but is not limited to the following probes: First, a dissolved oxygen probe (DO), which measures the dissolved oxygen content in water and reflects the health status of water; Second, a turbidity probe, which measures the turbidity of water and reflects the content of suspended particles in water. It is used to evaluate the transparency and pollution degree of water; Third, an oxidation-reduction potential (ORP) probe, which measures the oxidation-reduction potential of water and reflects the oxidation-reduction state of water.

[0036] It is used to evaluate the chemical stability and pollution degree of water. The pH probe, conductivity probe, dissolved oxygen probe, temperature probe and turbidity probe are used to monitor the basic parameters of water in real time.

[0037] The integrated sensor 1 includes but is not limited to the following sensors: First, a liquid level sensor, which monitors the liquid levels in the drug delivery tank, pretreatment tank, reaction tank and waste liquid bottle to prevent overflow or dryness. Ensure the accuracy of reagent addition and waste liquid treatment; Second, a flow sensor, which measures the flow rate of water samples in the sampling system to ensure precise control of the sampling volume. It is used for flow monitoring in the micro water pump 13 and pipeline system; Third, a pressure sensor, which monitors the pressure changes inside the system, such as the pressure output of the pump and the pressure in the pipeline. Ensure the stable operation of the system and avoid failures caused by overpressure or low pressure; Fourth, a position sensor, which monitors the position and attitude of the unmanned ship to ensure its operation on the predetermined path and perform accurate positioning. Combined with GPS or other positioning systems, realize the autonomous navigation and control of the unmanned ship; Fifth, a humidity sensor, which monitors the humidity inside the ship's hull to prevent excessive humidity from affecting the normal operation of electronic devices. It is used for monitoring the internal environment of the hull to protect sensitive devices; Sixth, a vibration sensor, which monitors the vibration of the unmanned ship to judge whether there is abnormal vibration or mechanical failure. It is used for health monitoring of the power system and structural components. Monitor the hull stability through the vibration sensor and pause the detection when the sway amplitude exceeds the threshold; Monitor the liquid level of the drug delivery tank 6 in real time and send a warning signal when the remaining amount is less than 10%; The data verification module compares the dispersion degree of the detection results of three parallel samples, and starts the re-inspection procedure when it exceeds 5%; Seventh, a battery power sensor, which monitors the remaining power of the lithium-ion battery system 15 to ensure that the unmanned ship has enough power to complete the task. It is used for power management to optimize the working time of the unmanned ship.

[0038] Using a position sensor and a vibration sensor, the position and operating status of the unmanned boat are monitored in real time to ensure that it travels along a predetermined path. By using a battery power sensor and a humidity sensor, the power status and internal environment of the unmanned boat are monitored to detect and solve potential problems in a timely manner.

[0039] The data from integrated probe 2, integrated probe 5, and integrated sensor 1 are processed by a central controller to generate a detailed water quality report. According to the analysis results, the piston movement distance of the dosing chamber is adjusted to ensure that the volume of the added reagent meets the requirements. Integrated probe and related sensors: Provide data support and optimize the dosing amount.

[0040] To achieve the automation process and safety of the unmanned boat, the communication module and the data transmission module are crucial components. It not only needs to be able to obtain measurement data in a timely manner and perform wireless transmission, but also needs to support functions such as remote control and on-site debugging. In some embodiments, there are also a communication module and a data transmission module to ensure that the unmanned boat can transmit and receive data in real time and efficiently and receive instructions, guaranteeing the automated operation and safety of the system.

[0041] The communication module and the data transmission module include a 5G module and a Bluetooth module, which are respectively used for long-distance transmission of water quality data and short-distance reception of instructions and on-site debugging.

[0042] The 5G module is used for long-distance transmission of water quality data to a remote server or data center. The water quality data collected by the unmanned boat (such as pH value, dissolved oxygen, conductivity, etc.) are transmitted to the remote server in real time for researchers or managers to view and analyze. Or upload the detection data to the cloud for storage, facilitating subsequent data processing and long-term preservation. When necessary, control instructions are sent to the unmanned boat through the 5G network to adjust its operating path or operation parameters.

[0043] The Bluetooth module is used for short-distance reception of instructions and on-site debugging and data extraction. Through Bluetooth connection, a handheld device (such as a mobile phone, tablet computer) is used to perform close-range operation and control of the unmanned boat.

[0044] Technicians can directly connect to the unmanned boat through the Bluetooth module to check the device status, set parameters, and troubleshoot faults. In the case of being unable to connect to the 5G network, data stored on the unmanned boat can be extracted through the Bluetooth module for convenient on-site data analysis and processing. The Bluetooth module has low power consumption, suitable for long-term standby and short-distance communication. The Bluetooth connection is simple and convenient, without complex configuration, easy to operate and use. It is suitable for short-distance communication within a range of several meters to dozens of meters, suitable for on-site debugging and close-range operation.

[0045] The automatic detection device disclosed in this application realizes real-time and accurate detection of heavy metal ions in complex water environments through a composite material hull, an automated sampling and detection system, and an efficient communication module. In addition, the automatic detection device may further include an environmental adaptability component, which includes an electromagnetic shielding layer, a structural reinforcement frame, etc.

[0046] Example 2

[0047] This embodiment details a real-time automatic detection method for heavy metal ions based on an unmanned boat, especially for the detection of hexavalent chromium ions (Cr(VI)) in water. This method uses the classical diphenylcarbazide spectrophotometric method and combines an automated control system to ensure efficient and accurate water quality monitoring in complex water environments.

[0048] In the existing technologies for detecting hexavalent chromium ions in water, there are traditional detection methods such as the diphenylcarbazide spectrophotometric method (national standard), UV detection liquid chromatography method, high performance liquid chromatography method, etc., as well as new methods such as ion chromatography-inductively coupled plasma mass spectrometry combined measurement method, HPLC-ICPMS combined detection method, on-line ion exchange - ICP-OES method, etc. However, the instruments and technologies used in all new detection methods are too expensive, cumbersome, and occupy a large space, and cannot be adapted to the scenario of being carried on an unmanned boat.

[0049] This application uses the diphenylcarbazide spectrophotometric method to roughly measure the collected water samples, which has high sensitivity and broad application prospects. The method is simple and economical, suitable for miniaturized equipment integration, especially suitable for the scenario of being carried on an unmanned boat.

[0050] The spectrophotometric method is a mature and effective method for detecting hexavalent chromium ions, with high sensitivity and broad application prospects. By measuring the absorption of light after forming a colored complex through a chemical reaction, the concentration of hexavalent chromium ions in water can be accurately detected. Although there are challenges such as interference and precision, these problems can be effectively overcome by optimizing reagents, selecting appropriate detection wavelengths, and standardizing operations to ensure accurate determination of the concentration of hexavalent chromium ions. At the same time, while achieving high-precision detection of Cr, the spectrophotometric method can also achieve the ability to synchronously detect other heavy metal ions.

[0051] Principle of the diphenylcarbazide spectrophotometric method: In an acidic environment, hexavalent chromium [Cr(VI)] usually exists as CrO 4 2- or Cr 2 O 7 2-It exists in the form of. When an acidic solution containing hexavalent chromium comes into contact with diphenylcarbazide (DPC), hexavalent chromium can oxidize diphenylcarbazide to diphenylcarbazone and form a purple-red complex with the reduction mixture of hexavalent chromium. This complex has a maximum absorption value at a specific wavelength, generally 540 nm, and its chromaticity is proportional to the content of hexavalent chromium, conforming to Lambert-Beer's law:

[0052] A = lg(1 / T) = Kbc.

[0053] Therefore, the concentration of hexavalent chromium can be quantitatively determined by measuring the absorbance of the solution.

[0054] The applicable conditions of this method are as follows:

[0055] First, control the concentration of hexavalent chromium ions within the range of 0.05 - 0.30 mol / L;

[0056] Second, control the iron content ≤ 1 mg / L to avoid the yellow color of the solution interfering with the test results.

[0057] A real-time automatic detection method for heavy metal ions based on an unmanned ship includes the following steps:

[0058] S1: Water sample collection

[0059] Through the micro water pump 13 and the telescopic sampling tube 3 carried by the unmanned ship, the water sample to be tested is extracted at the preset depth and transported to the pretreatment cabin; ensure that the water sample is representative and avoid the influence of surface floating substances and bottom sediments.

[0060] S2: Acquisition of environmental parameters and reagent calculation

[0061] Use the integrated probe 5 to obtain the water sample environmental data of the pretreatment cabin 4 in real time, and the central controller dynamically calculates the type and dosage of the added reagent according to the environmental data; ensure the accuracy of subsequent chemical reactions and avoid result deviations caused by environmental changes.

[0062] S3: Water sample pretreatment

[0063] Inject the pH adjustment reagent into the pretreatment cabin 4 through the piston-type dosing cabin 6 to adjust the pH value of the water sample to the range of 7.5 ± 0.5, then first add the measured auxiliary reagent to adjust the sample solution to an acidic environment, and finally add the color-developing reagent for pretreatment; ensure the smooth progress of the subsequent color reaction. Among them, the optional schemes of the pH adjustment reagent include nitric acid (analytical pure), sodium hydroxide solution, etc.; the optional schemes of the auxiliary reagent include sulfuric acid, phosphoric acid, etc.; the optional schemes of the color-developing reagent include diphenylcarbazide and acetone (for example: 0.25 g diphenylcarbazide: 100 mL acetone).

[0064] S4: Color reaction

[0065] Transfer the pretreated sample solution to the reaction chamber and let it stand for 3 - 10 minutes to complete the color reaction; allow hexavalent chromium to fully react with diphenylcarbazide to form a magenta complex.

[0066] S5: Sample solution dispensing

[0067] Dispense the reacted sample solution into a new waste liquid bottle and a standard colorimetric cell 9; synchronously rotate the waste liquid bottle axle 10 and the colorimetric cell axle 11 to ensure the orderly collection of waste liquid and the accurate transfer of water samples. Drive the synchronous rotation of the waste liquid bottle axle 10 and the colorimetric cell axle 11 through a motor, which also includes driving the axle to rotate a predetermined angle, verifying the alignment accuracy of the accommodation slot position by an optical sensor, and ensuring no leakage during the dispensing process by a pneumatic sealing device.

[0068] S6: Spectral analysis

[0069] Lower the lifting partition board to form a closed light path, eliminate environmental light interference by an automatic zero - adjustment module, and perform noise suppression processing by taking the average of three consecutive measurements. Use a UV - visible spectrophotometer 12 to measure the absorbance value of the solution in the colorimetric cell 9 at a wavelength of 540 nm; quantitatively determine the concentration of hexavalent chromium according to the absorbance value.

[0070] S7: Data processing and calculation

[0071] Based on the pre - stored standard curve equation:

[0072] y = km + b

[0073] Among them, in the standard curve equation:

[0074] y is the absorbance value, k is the slope of the fitting straight line, m is the concentration of hexavalent chromium, and b is the intercept of the fitting straight line; the values of parameters k and b need to be determined based on the results of simulation experiments in the laboratory and establishing a fitting curve.

[0075] According to the photometric value data detected by the unmanned ship in the actual environment, form a calculation formula for calculating the concentration of hexavalent chromium ions:

[0076] m=(y - b) / k

[0077] Estimate the content of hexavalent chromium concentration in the collected sample solution.

[0078] When calculating the concentration model in S7, when the detected value exceeds the linear range of the standard curve, the following processing is automatically triggered: control the sampling system to adjust the dilution factor D; re - execute the detection process of S1 - S7; mark the secondary dilution in the detection report.

[0079] S8: Data transmission and control. The detection data or the final detection value is transmitted back in real time through the 5G communication module, and the colorimetric cuvette wheel shaft 11 is controlled to switch to the next group of detection units. Ensure the timely transmission of data and the continuous operation of the system.

[0080] The above are only some embodiments of the present application and are not intended to limit the present application. For those skilled in the art, various changes and modifications can be made to the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the protection scope of the present application.

Claims

1. A real-time automatic detection device for heavy metal ions based on an unmanned ship, characterized in that: It comprises a hull, a power system mounted on the hull, a water sample collection module, a communication module and a data transmission module (14), a monitoring and control unit and an integrated detection system; wherein: The integrated detection system comprises: A plurality of drug administration chambers (6), each of which stores reagents and is equipped with a volume control system; The pretreatment chamber (4) is used to hold the collected water sample. Each of the drug administration chambers (6) can selectively add a reagent to the pretreatment chamber (4), and the amount of the reagent added is accurately controlled by the volume control system. The pretreatment chamber (4) pre-treats the water sample after the reagent is added. A reaction chamber (7), wherein the reaction chamber (7) is used to contain the water sample pretreated by the pretreatment chamber (4) and to react therein; A plurality of cuvettes (9) for receiving the water sample to be tested in the reaction chamber (7); and The UV-visible spectrophotometer (12) performs spectral analysis on the water sample in the cuvette (9) to determine the concentration of heavy metal ions.

2. The detection device according to claim 1, characterized in that: The integrated detection system also includes: a plurality of waste liquid bottles (8) for collecting waste liquid from the reaction chamber (7); A waste liquid bottle axle (10) is used to drive the position switching of a plurality of waste liquid bottles (8) to achieve the subpackaging and storage of waste liquid; The cuvette wheel shaft (11) is used to drive the position switching of the plurality of cuvettes (9) to receive different water samples to be detected and to detect the different water samples in the plurality of cuvettes (9) in sequence.

3. The detection device according to claim 2, characterized in that: The integrated detection system also includes: The waste liquid bottle axle (10) and the cuvette axle (11) adopt a synchronous rotation mechanism, each of which is provided with a plurality of independent accommodating slots for accommodating a plurality of waste liquid bottles (8) and a plurality of cuvettes (9), and the continuous storage and switching of the detection samples are realized through motor drive.

4. The detection device according to claim 1, characterized in that: The medication capsule (6) comprises a glass fiber reinforced plastic cylindrical liner container, wherein a plurality of medication capsules (6) respectively store a pH adjusting reagent, an auxiliary reagent and a color developing reagent, wherein a piston is arranged in the liner container, and the addition amount is calculated by measuring the piston displacement to achieve precise volume control.

5. The detection device according to claim 1, characterized in that: The ultraviolet-visible spectrophotometer (12) comprises: The optical path isolation plate can be raised and lowered to form a closed optical channel during measurement; A rotary cuvette positioning mechanism is mechanically coupled to the cuvette axle (11) system; 540nm wavelength dedicated detection channel and supporting optical components.

6. The detection device according to claim 1, characterized in that: The hull structure comprises an aluminum alloy shell (20), the outer surface of which is coated with a corrosion-resistant and electromagnetic interference-resistant coating (40), and the inner surface of which is wrapped with a carbon fiber and glass fiber filling layer to form an insulating layer (30) of a composite material structure; The power system (15) comprises a lithium-ion battery system (15) and a tail propeller powered by the lithium-ion battery system (15); The water sample collection module comprises a micro water pump (13) and a retractable sampling tube (3); The pretreatment chamber (4) is also equipped with a stirrer (41) to achieve uniform mixing of the reagent and solution added to the pretreatment chamber (4); The monitoring and control unit comprises an integrated sensor (1), an integrated probe (5) and an integrated probe head (2), and its detection data is fed back to the central controller in real time for dynamic adjustment of pre-processing parameters; The communication module and data transmission module (14) include a 5G long-range transmission module and a Bluetooth short-range control module.

7. A real-time automatic detection method for heavy metal ions based on an unmanned ship, characterized in that: The unmanned boat moves to the target waters, and the automatic detection method comprises the following steps: S1: water sample collection; extracting the water sample to be tested at a preset depth through a micro water pump (13) and a sampling tube (3) and transporting it to a pretreatment chamber (4); S2: Acquisition of environmental parameters and calculation of reagents; using the integrated probe (5) to obtain the environmental data of the water sample in the pretreatment chamber (4) in real time, the central controller dynamically calculates the type and amount of added reagents based on the detected environmental data; S3: water sample pretreatment: adding a pH adjusting reagent to the water sample until it reaches a preset value, and then adding corresponding amounts of auxiliary reagents and color developing reagents in sequence; S4: color development reaction; transferring the pre-treated sample solution to the reaction chamber (7) and leaving it for a preset time to allow it to fully react; S5: sample solution injection; injecting the reacted sample solution into the corresponding standard cuvette (9) to form a group of detection units; S6: spectral analysis; using a UV-visible spectrophotometer (12) to measure the absorbance of the solution in the cuvette (9) at a preset wavelength; S7: data processing and calculation; calculating the heavy metal ion concentration according to the preset standard curve equation of absorbance and concentration; S8: Data transmission and control; the final detection value is transmitted back in real time through the communication module (14), and the cuvette wheel shaft (11) is controlled to switch to the next group of detection units.

8. The method according to claim 7, characterized in that: S3: water sample pretreatment, The pH adjusting reagent includes: Nitric acid (analytical grade) and sodium hydroxide solution; The pH value of the water sample in the pretreatment chamber (4) is adjusted to the range of 7.5±0.

5. The auxiliary reagents include: Sulfuric acid (analytical grade), phosphoric acid (analytical grade); The color developing reagent is a solution of diphenylcarbazide and acetone, wherein: The ratio of diphenylcarbazide to acetone is: 0.25g diphenylcarbazide: 100mL acetone.

9. The method according to claim 7, characterized in that , In the above S5, the sample liquid dispensing further comprises: injecting the waste liquid after the reaction into the waste liquid bottle (8), and driving the waste liquid bottle axle (10) and the cuvette axle (11) to rotate synchronously by a motor, so that the waste liquid bottle (8) and the cuvette (9) are moved to a predetermined position; or / and In S6: the spectral analysis further comprises the following steps: S61, an optical sensor verifies the accuracy of the receiving slot relative to the position to be measured by the photometer (110); S62, the lifting isolation plate descends to form a closed light channel to eliminate ambient light interference.

10. The method according to claim 7, characterized in that The automatic detection method further comprises: S9: abnormality detection, the abnormality detection includes: The stability of the hull is monitored through vibration sensors, and detection is suspended when the shaking amplitude exceeds the threshold; Real-time monitoring of the liquid level of the medication chamber (6), and sending an early warning signal when the remaining amount is less than 10%; The data verification module compares the discreteness of the test results of three parallel samples, and starts the re-test procedure when it exceeds 5%.

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