Cruise type total phosphorus automatic analyzer

Abstract

The utility model belongs to the technical field of equipment for detecting total phosphorus in a water body, and particularly relates to a cruise type total phosphorus automatic analyzer. According to the utility model, unmanned cruise, automatic sampling and flow analysis technologies are combined, so that the function of measuring the total phosphorus in the water body through cruise type flow analysis is realized, and the detection result is efficient and accurate. The method can realize rapid and automatic digestion and detection of total phosphorus, is associated with the navigation track of the unmanned ship, presents the distribution state of total phosphorus in the water body in real time, and is beneficial to improving the accuracy and timeliness of environment monitoring. The influence of interferents in environmental water on subsequent reaction is effectively solved by firstly entering the reducing agent, and no obvious difference exists between actual test and on-machine detection results after manual pretreatment. The low-content total phosphorus in the water body can be accurately measured, and the result is matched with the manual detection result in a laboratory. By adopting the design of automatic sample injection switching, calibration can be carried out according to the detection condition during operation, manual calibration in shore is not needed, the analysis efficiency is improved, and the detection precision is ensured.

Description

TECHNICAL FIELD

[0001] The utility model belongs to water body total phosphorus detection equipment technical field, concretely relates to a cruise type total phosphorus automatic analyzer. BACKGROUND

[0002] With the continuous development of economy, the demand of people for ecological environment quality is increasing, and the requirement of environmental management for monitoring work is also increasing. Among them, the daily monitoring, the emergency monitoring of sudden environmental pollution events, the analysis of section encryption and the increase of positioning quantity in environmental scientific research monitoring make the monitoring workload increase. In addition, affected by the natural geographical environment, the sampling personnel are often in a dangerous environment, and their life safety is threatened, which has become a increasingly prominent problem. Therefore, a standardized and reasonable, safe and reliable automatic cruise analysis technology is urgently needed to meet the increasingly complex on-site environmental monitoring needs.

[0003] At present, the cruise monitoring device on the market is mainly optical, electronic and sonar sensor, which lacks the ability to analyze complex projects and is insufficient in monitoring the comprehensive indicators of water quality such as total phosphorus. The in-situ total phosphorus analysis of water body can use sequential injection-photometric analysis method (SIA), but the sequential injection device used in this method runs slowly, and needs to be cleaned regularly to avoid pollution. Only 4-6 points can be tested in 1 hour, which cannot continuously monitor the total phosphorus in water, is not conducive to quickly grasp the real-time data indicators of water body, and cannot quickly track important spatial and temporal data such as pollution formation, peak and transfer. The working principle of other types of sensors adopts optical absorption method, and the particles and turbidity in water will affect the detection results. There are also double optical path systems to deduct the matrix interference, but the lower limit of the total phosphorus content detected is large, which cannot meet the detection requirements of surface water.

[0004] Flow injection analysis technology (FIA) is a new flow analysis technology created by Danish scientists in 1974, which is a modern analysis technology for automatic online processing and determination of solution. It has a series of advantages such as fast analysis speed, high accuracy and precision, simple equipment and operation, strong universality, and small sample and reagent consumption. Ruzicka et al. defined flow injection analysis in the second edition of their monograph in 1988 as follows: injecting a clear fluid zone into a flow path, dispersing in a continuous non-isolated carrier fluid to form a concentration gradient, and obtaining information from the concentration gradient.

[0005] In summary, the use of flow injection analysis technology can meet the cruise intensive and rapid detection requirements, and its analysis speed, frequency, accuracy and sensitivity can well meet the detection requirements of surface water. CONTENT OF THE UTILITY MODEL

[0006] The utility model discloses in order to overcome the cruise type water body total phosphorus monitoring device in the prior art for total phosphorus etc. water quality comprehensive index monitoring ability is insufficient, can not sustain, automatic monitoring water body total phosphorus, it is difficult to fast, accurate, real-time detection's defect, provides a cruise type total phosphorus automatic analyzer to overcome above-mentioned defect.

[0007] In order to realize the above-mentioned purpose of the application, the utility model realizes through the following technical schemes:

[0008] A cruise type total phosphorus automatic analyzer, comprising:

[0009] Sliding switch sampling module, the sliding switch sampling module includes liquid storage chamber and the reagent bin for containing reaction reagent, the liquid storage chamber includes the sample pool for storing the sample to be measured and the calibration cavity for storing standard sample, the top of liquid storage chamber is provided with sampling device, sampling device moves back and forth along horizontal direction and is linked with sample pool or calibration cavity communication;

[0010] Shipborne flow analysis module, the shipborne flow analysis module includes the digestion processing device for heating and digestion to the sample to be measured, and the cooling device for cooling the sample to be measured after digestion is connected with digestion processing device through pipeline, the output end of cooling device is connected through pipeline and is provided with color development heating device for the color development reaction to the sample to be measured after cooling;

[0011] Optical detection module, the optical detection module includes the reference light path for the sample to be measured after digestion without adding color developing agent and flowing, the detection light path for the sample to be measured after digestion adding color developing agent and flowing and the detector for collecting the photoelectric signal of reaction product, the output end of reference light path and detection light path all are linked with detector communication;

[0012] Peristaltic pump for driving the sample to be measured and reaction reagent into flow path and carrying out reaction;

[0013] Wherein, the sliding switch sampling module, shipborne flow analysis module, optical detection module and peristaltic pump are communicated through pipeline.

[0014] The utility model discloses a sliding switch sampling module, shipborne flow analysis module, optical detection module and peristaltic pump are included. Among them, sliding switch sampling module, shipborne flow analysis module, optical detection module and peristaltic pump are connected through pipeline intercommunication between. Sliding switch sampling module includes liquid storage chamber and the reagent bin for containing reaction reagent, and the liquid storage chamber includes the sample cell for storing the sample to be measured and the calibration cavity for storing the standard sample. The top of liquid storage chamber is provided with sampling device, and the sampling device moves back and forth along the horizontal direction and is connected with the sample cell or the calibration cavity. The shipborne flow analysis module includes the digestion processing device for heating and digestion to the sample to be measured, and the cooling device is connected with the digestion processing device through the pipeline and is used for cooling the sample to be measured after digestion. The output end of cooling device is connected through the pipeline and is provided with the color development heating device for the color development reaction to the sample to be measured after cooling. The optical detection module includes the reference light path for the sample to be measured after digestion without adding color developing agent, the detection light path for the sample to be measured after digestion adding color developing agent and the detector for collecting the photoelectric signal of reaction product. The output end of reference light path and detection light path is connected with the detector. Peristaltic pump is used to drive the sample to be measured and reaction reagent into flow path and carry out the reaction.

[0015] The utility model discloses a sliding switch sampling module, in the calibration cavity of preset standard sample and the sample cell containing actual water body sample automatic switching, effectively improve the analysis frequency and accuracy. Sampling flow path connection switch valve, when switch valve turns the calibration cavity containing standard sample can draw standard sample and carry out calibration, when switch valve turns the sample cell containing actual water body sample can detect water sample. The unmanned ship total phosphorus flow analysis sample collection switch design can realize the automatic switching of built-in calibration point in the ship body and the sample of cabin outside.

[0016] Meanwhile, the utility model discloses a shipborne flow analysis module, and total phosphorus in the sample to be measured is digested as the measured orthophosphate in the flow injection closed system after high temperature heating and ultraviolet irradiation, mixes after quantification and color developing agent, reducing agent and forms new color developing substance, thereby realizing automatic detection. Through heating digestion to the sample to be measured and automatic liquid adding color development reaction to the component after decomposition, the reaction process has heating insulation function, effectively avoids the influence of complex external environment on the reaction, and it is helpful to guarantee detection precision, accuracy.

[0017] In addition, the utility model discloses an optical detection module, and a double light path (namely reference light path and detection light path) is designed, has the structure of shunting, can divide liquid path into two paths and detect absorbance respectively, and carries out ratio calculation and deducts the influence of matrix effect on analysis result.

[0018] Existing patrol monitoring technologies mostly utilize photoelectric and sonar sensors, primarily monitoring conventional indicators such as pH, temperature, dissolved oxygen, turbidity, and conductivity of water bodies. Monitoring data can be automatically matched with latitude and longitude, offering the advantage of rapid visualization of the overall quality of environmental water bodies. However, in actual environmental water sample monitoring, core indicators such as total phosphorus, total nitrogen, ammonia nitrogen, and permanganate index are often used to determine water pollution levels; these are core monitoring items for comprehensive pollutants in environmental monitoring. However, these monitoring items often require complex sample processing, making accurate measurement difficult with photoelectric sensors. Therefore, automated monitoring cannot be achieved in field environments or on small unmanned patrol platforms, failing to meet the needs of various application scenarios. Generally, samples must be retrieved and tested in a laboratory, resulting in data lag, which is detrimental to emergency pollution monitoring. Furthermore, samples are easily contaminated or expired, leading to inaccurate test results and failing to fully leverage the advantages of real-time data upload and precise analysis point matching during unmanned surface vessel (USV) patrol monitoring.

[0019] Flow injection analysis (FIA) offers significant advantages for rapid and automated detection of total phosphorus in laboratory settings. Through a closed-loop liquid reaction, the sample undergoes treatment steps such as high temperature, ultraviolet irradiation, and ion reduction during flow, ultimately mixing with a colorimetric reagent to form the analyte. This analyte is then automatically measured in a detection cell, ensuring accuracy and reliability. However, these instruments are generally complex, bulky, and power-consuming. Their optical monitoring components are also sensitive to environmental conditions, making them unsuitable for field use and preventing unmanned, continuous monitoring.

[0020] The utility model discloses a cruise, automatic sampling, flow analysis technology is combined, realized the function of cruise type flow analysis determination total phosphorus in water body, and the detection result is efficient and accurate. Can realize total phosphorus fast automatic digestion, detection flow, and simultaneously with unmanned ship navigation track association, real-time presentation total phosphorus distribution state in water body, is favorable to promote environmental monitoring accuracy, timeliness. Compared with the prior art that uses photoelectric sensor (its principle is direct photometric absorption or electric signal change) and can not determine low concentration total phosphorus signal in water sample, the utility model discloses flow injection analysis technology through heating, ultraviolet digestion and its high sensitivity photometric detector, can accurately determine low content total phosphorus in water body, and the result is consistent with laboratory manual detection. Meanwhile, unlike the flow analysis technology of traditional laboratory, the internal flow path design of the shipborne flow analysis loading device of the utility model effectively solves the influence of interference in environmental water on subsequent reaction by entering the reducing agent first. There is no obvious difference in the detection result after actual testing and manual pretreatment. In addition, compared with other shipborne equipment, the utility model discloses sample automatic switching design, which can calibrate during operation according to the detection condition, without manual calibration by landing, which helps to improve analysis efficiency and ensure detection accuracy. In addition, by setting the track cruise, the utility model can automatically collect and analyze total phosphorus in water body, and the detection result is bound to the track, realizing real-time display of pollution track without post-processing data.

[0021] As preferred, the calibration cavity is provided with several calibration tubes for standard sample flow, and the number of calibration tubes is at least five.

[0022] As further preferred, the calibration tube is further provided with a filtering device.

[0023] By providing at least five calibration tubes, each of which is provided with a calibration liquid of different concentration, a standard sample curve of different concentration gradient is further obtained. Meanwhile, different calibration tubes can be loaded with standard samples of different concentrations, which helps to meet the calibration requirements of different measurement ranges and accuracies. In addition, by designing multi-point calibration, the calibration accuracy is improved, and the calibration efficiency is enhanced.

[0024] As preferred, the sample injection device comprises an injection device in sliding connection with a liquid storage chamber, one end of the injection device is connected with a driving assembly for driving the injection device to move back and forth in the horizontal direction, and the other end of the injection device is connected with a peristaltic pump.

[0025] As further preferred, the driving assembly comprises a guide rail connected with the injection device and a motor arranged on the guide rail and capable of driving the injection device to move back and forth in the horizontal direction of the guide rail.

[0026] Through the above setting, the injection device is communicated with the calibration cavity at the initial position, and the standard sample curve is obtained after the calibration of the calibration tube after the standard sample injection is completed. Then the motor is started to drive the injection device to move to the corresponding position along the guide rail in the horizontal direction, so that the injection device is communicated with the sample cell, and then the sliding switching to the water sample collection is realized, without manual replacement of the sample pipeline, which helps to reduce the operation complexity. At the same time, the water body detection can be carried out after the standard sample calibration at any place without manual intervention, so that the problem of easy fluctuation of the liquid inlet pump tube for a long time is overcome, and the detection efficiency and accuracy are greatly improved.

[0027] As a further preferred, the pump speed of the peristaltic pump is 1-99 r / min.

[0028] As a preferred, the digestion treatment device comprises a heater for heating the sample to be measured, and an ultraviolet digestion tube is wound outside the heater for light digestion of the sample to be measured.

[0029] As a further preferred, the heater is an electric heating metal rod, and the ultraviolet digestion tube is made of high-temperature resistant quartz material.

[0030] The heater is an electric heating metal rod, and a high-temperature resistant PTFE material pipeline is wound thereon. The sample to be measured is decomposed by heat in the pipeline to form detectable substances (PO3 4- ). At the same time, the analysis pipeline is improved to be pre-mixed with the reducing agent, effectively solving the complex matrix interference in the environmental water body, and the automatic analysis of the sample to be measured can be completed without manual intervention, and the detection result is accurate and reliable. In addition, the outer layer of the heater is wound with an ultraviolet digestion tube, which is wound with high-temperature resistant quartz material, which can directly irradiate ultraviolet energy on the heated sample to be measured, further improving the digestion efficiency. In addition, the ultraviolet winding type heater design can effectively reduce the volume of the digestion treatment device, which is beneficial to the installation of portable devices.

[0031] The reaction reagent is driven by the peristaltic pump, and the reaction reagent is injected into the reaction cell to react with the measured substance in the digested sample. The reaction cell has a heating and insulation function, which can effectively avoid the influence of environmental temperature change on the reaction consistency.

[0032] As a preferred, a check valve and a reference cell for containing the digested sample without developing agent are sequentially arranged on the flow path of the reference light path, and the input end of the check valve is connected with the peristaltic pump.

[0033] By arranging the check valve, the backflow of the liquid caused by the pressure change after stopping the pump into the reference cell can be effectively prevented, which further affects the detection result.

[0034] Preferably, a detection cell for containing the digested sample containing the chromogenic agent is arranged in the flow path of the detection light path, and the input end of the detection cell is connected with the peristaltic pump.

[0035] The well-mixed sample enters the fluid detection cell, which is placed in the optical detection module. The optical detection module includes a reference light path for the flow of the sample without the chromogenic agent and after digestion, and a detection light path for the flow of the sample with the chromogenic agent and after digestion, and further includes a detector for collecting the photoelectric signal of the reaction product, and the output ends of the reference light path and the detection light path are both connected with the detector. The reference light path does not pass the chromogenic reagent into the detector, and only identifies the baseline of the reaction reagent. After the sample is mixed with the chromogenic reagent, the reaction product enters the detection light path, and the detector identifies the photoelectric signal of the reaction product. Finally, the photoelectric signal data of the detection cell and the photoelectric signal data of the reference cell are collected by the detector, and the final detection result is obtained by calculating and processing by the ratio method. After the two groups of data are collected, the ratio method is used to calculate as follows:

[0036]

[0037] Wherein: 、 are the primary and secondary wavelength molar absorption coefficients, L is the optical path, and C is the concentration of the sample to be tested. This method can effectively eliminate the detection errors caused by turbidity, color and other factors.

[0038] Preferably, the shipborne flow analysis module further comprises a quantitative valve, a mixing device I for mixing the sample to be tested, the digestion liquid and the oxidizing agent is arranged between the quantitative valve and the digestion treatment device, the input end of the quantitative valve is connected with the peristaltic pump, the output end of the quantitative valve is connected with the mixing device I, and the output end of the mixing device I is connected with the digestion treatment device.

[0039] The peristaltic pump drives the sample to be tested into the quantitative valve and then into the mixing device I. The peristaltic pump drives the digestion liquid into the mixing device I through the switching valve I and mixes with the sample to be tested, so as to obtain the sample to be tested after acid adjustment. The peristaltic pump drives the oxidizing agent into the mixing device I through the switching valve II and mixes with the sample to be tested after acid adjustment, and finally enters the digestion treatment device for mixing and digestion.

[0040] Preferably, the shipborne flow analysis module further comprises a mixing device II, the input end of the mixing device II is connected with the peristaltic pump and the cooling device respectively, the output end of the mixing device II is connected with the reference cell, and the mixing device II and the reference cell are further provided with a switching valve III.

[0041] The sample to be measured after high-temperature digestion passes through a cooling device and enters a mixer II, and a peristaltic pump drives a reducing agent to enter the mixer II and mix with the sample to be measured after high-temperature digestion, and then enters a reference cell through a switching valve III.

[0042] Preferably, the shipborne flow analysis module further comprises a mixer III, an input end of the mixer III being connected with the peristaltic pump and the switching valve III respectively, an output end of the mixer III being connected with a color developing heating device, and an output end of the color developing heating device being connected with a detection light path.

[0043] The switching valve III is switched to connect the output end of the switching valve III with the input end of the mixer III, the peristaltic pump drives a color developing agent to enter the mixer III and mix with the sample to be measured after digestion, and then enters the color developing heating device together to generate a stable blue compound.

[0044] Therefore, the utility model has the following beneficial effects:

[0045] (1) The utility model discloses the combination of unmanned cruise, automatic sampling and flow analysis technology, realizes the function of cruise type flow analysis determination of total phosphorus in water body, and the detection result is efficient and accurate.

[0046] (2) Compared with the prior art that cannot determine the low-concentration total phosphorus signal in water sample by using a photoelectric sensor (the principle is direct light absorption or electric signal change), the utility model adopts flow injection analysis technology to accurately determine the low-content total phosphorus in water body through heating, ultraviolet digestion and a high-sensitivity photometric detector, and the detection result is consistent with the manual detection result in the laboratory.

[0047] (3) Unlike the traditional flow analysis technology in the laboratory, the internal flow path design of the shipborne flow analysis loading device of the utility model effectively solves the influence of interference substances in the environment water on subsequent reactions by entering the reducing agent first, and actual test shows that there is no obvious difference between the detection result after manual pretreatment and the detection result on the machine.

[0048] (4) Compared with other shipborne equipment, the utility model adopts automatic sampling switching design, can calibrate according to the detection condition during operation, does not need to be landed for manual calibration, helps to improve the analysis efficiency and ensure the detection precision.

[0049] (5) When the track cruise is set, the utility model can automatically collect and analyze the total phosphorus in water body, the detection result is bound with the track, realizes real-time display of the pollution track, and does not need post-processing of data. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1The flow analysis process diagram on the ship.

[0051] Figure 2 The structural diagram of the sliding switching sample injection module.

[0052] Figure 3 The connection structure diagram of the sample injection device and the sample cell and the calibration cavity.

[0053] Figure 4 The connection structure diagram of the digestion treatment device and the cooling device.

[0054] Figure 5 The structural diagram of the optical detection module.

[0055] In the figure: sliding switching sample injection module 1; liquid storage chamber 2; reagent bin 3; sample cell 4; calibration cavity 5; sample injection device 6; shipborne flow analysis module 7; digestion treatment device 8; cooling device 9; color development heating device 10; optical detection module 11; reference light path 12; detection light path 13; detector 14; peristaltic pump 15; calibration tube 16; injection device 17; driving assembly 18; heater 19; ultraviolet digestion tube 20; check valve 21; reference cell 22; detection cell 23; quantitative valve 24; mixer I 25; mixer II 26; switching valve III 27; mixer III 28; switching valve I 29; switching valve II 30. DETAILED DESCRIPTION

[0056] The utility model will be further described below in combination with the drawings and specific embodiments. The person skilled in the art will be able to realize the utility model based on these descriptions. In addition, the embodiments of the utility model involved in the following description are generally only a part of the embodiments of the utility model, not all the embodiments. Therefore, based on the embodiments in the utility model, all other embodiments obtained by the person skilled in the art without creative labor shall belong to the protection scope of the utility model.

[0057] Embodiment 1

[0058] As Figures 1-5As shown, the utility model discloses sliding switch sampling module 1, shipborne flow analysis module 7, optical detection module 11 and peristaltic pump 15. Among them, sliding switch sampling module 1, shipborne flow analysis module 7, optical detection module 11 and peristaltic pump 15 are communicated through pipeline between the interconnection. Sliding switch sampling module 1 includes liquid storage chamber 2 and reagent bin 3 for containing reaction reagent, and liquid storage chamber 2 includes sample cell 4 for storing the sample to be measured and calibration cavity 5 for storing standard sample. The top of liquid storage chamber 2 is provided with sampling device 6, and sampling device 6 moves back and forth along the horizontal direction and is communicated with sample cell 4 or calibration cavity 5. Shipborne flow analysis module 7 includes digestion treatment device 8 for heating and digesting the sample to be measured, and cooling device 9 connected with digestion treatment device 8 through pipeline and used for cooling the sample to be measured after digestion. The output end of cooling device 9 is connected through pipeline and is provided with color development heating device 10 for carrying out color development reaction on the sample to be measured after cooling. Optical detection module 11 includes reference light path 12 for the flow of the sample to be measured after digestion without adding color developing agent, detection light path 13 for the flow of the sample to be measured after digestion with adding color developing agent and detector 14 for collecting the photoelectric signal of the reaction product. The output end of reference light path 12 and detection light path 13 is communicated with detector 14. Peristaltic pump 15 is used to drive the sample to be measured and reaction reagent into the flow path and carry out reaction.

[0059] The utility model discloses sliding switch sampling module 1, and the calibration cavity 5 of preset standard sample is switched automatically in the sample cell 4 containing actual water body sample, and the analysis frequency and accuracy are effectively improved. Sampling flow path connection switch valve, when the switch valve is turned to the calibration cavity 5 containing standard sample, can suck standard sample and calibrate, when the switch valve is turned to the sample cell 4 containing actual water body sample, can detect water sample. The total phosphorus flow analysis sample collection switching design for unmanned ship can realize the automatic switching of the built-in calibration point in the ship body and the sampling of the cabin outside.

[0060] Meanwhile, the utility model discloses shipborne flow analysis module 7, and total phosphorus in the sample to be measured is digested as the measured orthophosphate in the flow injection closed system after high temperature heating and ultraviolet irradiation, and after quantification, mixes with color developing agent and reducing agent to form new color developing substance, thereby realizing automatic detection. The sample to be measured is heated and digested, and the components after decomposition are automatically added and color developed, and the reaction process has heating and insulation functions, effectively avoids the influence of complex external environment on the reaction, and helps to guarantee the detection precision and accuracy.

[0061] In addition, the utility model discloses optical detection module 11, and a double light path (namely reference light path 12 and detection light path 13) is designed, has the structure of shunting, can divide liquid path into two paths and detect absorbance respectively, and carries out ratio calculation and deducts the influence of matrix effect on analysis result.

[0062] The utility model discloses a cruise type flow analysis determination water body total phosphorus function is realized to the combination of unmanned cruise, automatic sample introduction, flow analysis technology, and the detection result is efficient and accurate. Can realize total phosphorus quick automatic digestion, detection flow, and simultaneously with unmanned ship navigation track association, real -time presentation water body total phosphorus distribution state, is favorable to promote environmental monitoring accuracy, timeliness. Compared with the current adoption photoelectric sensor etc. (its principle is direct photometric absorption or electric signal change) and can not determine low concentration total phosphorus signal in water sample, the utility model discloses flow injection analysis technology through heating, ultraviolet digestion and its high sensitivity photometric detector 14, can accurately determine low content total phosphorus in water body, and the result is consistent with laboratory manual detection. Meanwhile, unlike traditional laboratory flow analysis technology, the internal flow path design of the shipborne flow analysis loading device of the utility model effectively solves the influence of interference substances existing in the environment water on the subsequent reaction by entering the reducing agent first. There is no obvious difference in the detection result after actual testing and manual pretreatment. In addition, compared with other shipborne equipment, the utility model discloses sample introduction automatic switching design, which can calibrate according to the detection condition during operation, without manual calibration by landing, which helps to improve analysis efficiency and ensure detection accuracy. In addition, by setting the track cruise, the utility model can automatically collect and analyze total phosphorus in water body, and the detection result is bound with the track, realizing real-time display of pollution track without post-processing data.

[0063] As an implementation manner, the reaction reagent contained in the reagent bin 3 includes a digestion solution, an oxidizing agent, a reducing agent and a color developing agent. The digestion solution is a sulfuric acid solution, the oxidizing agent is a potassium permanganate solution, the reducing agent is an ascorbic acid solution, and the color developing agent is an ammonium molybdate solution.

[0064] As an implementation manner, a plurality of calibration tubes 16 for standard sample flow are arranged in the calibration cavity 5, and the number of the calibration tubes 16 is at least five.

[0065] As another implementation manner, a filtering device is further arranged in the calibration tube 16.

[0066] By arranging at least five calibration tubes 16, different concentrations of calibration solutions are arranged in each calibration tube 16, so that different concentration gradient standard sample curves are further obtained. Meanwhile, different calibration tubes 16 can be loaded with standard samples of different concentrations, which helps to meet the calibration requirements of different measurement ranges and accuracies. In addition, by designing multi-point calibration, the calibration accuracy is improved, and the calibration efficiency is enhanced.

[0067] As an implementation, the sample injection device 6 comprises an injection device 17 which is slidingly connected with the sample storage chamber 2. One end of the injection device 17 is connected with a driving assembly 18 for driving the injection device 17 to move back and forth in the horizontal direction, and the other end of the injection device 17 is connected with the peristaltic pump 15.

[0068] As an implementation, the driving assembly 18 comprises a guide rail connected with the injection device 17 and a motor arranged on the guide rail and capable of driving the injection device 17 to move back and forth in the horizontal direction of the guide rail.

[0069] Through the above arrangement, the injection device 17 is in communication with the calibration cavity 5 at the initial position, and the calibration is performed after the standard sample injection of the calibration tube 16 is completed, so as to obtain the standard sample curve. Then the motor is started to drive the injection device 17 to move to the corresponding position in the horizontal direction of the guide rail, so that the injection device 17 is in communication with the sample cell 4, and then the sliding switching to the water sample collection is realized, without the need for manual replacement of the sample pipeline, which helps to reduce the operation complexity. At the same time, the standard sample calibration can be performed at any place before the water body detection, without manual intervention, so as to overcome the problem that the liquid inlet pump tube is easily fluctuated for a long time, and the detection efficiency and accuracy are greatly improved.

[0070] As another implementation, the pump speed of the peristaltic pump 15 is 1-99 r / min.

[0071] As an implementation, the digestion treatment device 8 comprises a heater 19 for heating the sample to be tested, and an ultraviolet digestion tube 20 for light digestion of the sample to be tested is arranged outside the heater 19.

[0072] As another implementation, the heater 19 is an electric heating metal rod, and the ultraviolet digestion tube 20 is made of high-temperature-resistant quartz material.

[0073] The heater 19 is an electric heating metal rod, and a high-temperature-resistant PTFE material pipeline is wound thereon. The sample to be tested is decomposed by heat in the pipeline to form detectable substances (PO43-). 4- At the same time, the analysis pipeline is improved to be pre-mixed with a reducing agent, effectively solving the complex matrix interference in the environmental water body, and the automatic analysis of the sample to be tested can be completed without manual intervention, and the detection result is accurate and reliable. In addition, the outer layer of the heater 19 is wound with the ultraviolet digestion tube 20, which is wound with high-temperature-resistant quartz material, and the ultraviolet energy can be directly irradiated on the heated sample to be tested, further improving the digestion efficiency. In addition, the ultraviolet winding type heater 19 design can effectively reduce the volume of the digestion treatment device 8, which is beneficial to the installation of portable devices.

[0074] The reaction reagent is driven by the peristaltic pump 15, injected into the reaction cell and reacted with the measured substance after digestion of the sample. The reaction cell has a heating and insulation function, which can effectively avoid the influence of environmental temperature changes on the consistency of the reaction.

[0075] As an embodiment, a check valve 21 and a reference cell 22 for containing the measured sample after digestion without developing agent are sequentially arranged on the flow path of the reference light path 12. The input end of the check valve 21 is connected with the peristaltic pump 15.

[0076] By arranging the check valve 21, the liquid backflow caused by pressure changes after stopping pumping into the reference cell 22 can be effectively prevented, further affecting the detection results.

[0077] As an embodiment, a detection cell 23 for containing the measured sample after digestion containing developing agent is arranged on the flow path of the detection light path 13. The input end of the detection cell 23 is connected with the peristaltic pump 15.

[0078] The fully mixed measured substance enters the fluid detection cell 23, and the detection cell 23 is arranged in the optical detection module 11. The optical detection module 11 includes a reference light path 12 for the flow of the measured sample after digestion without adding developing agent and a detection light path 13 for the flow of the measured sample after digestion with developing agent, and also includes a detector 14 for collecting the photoelectric signal of the reaction product. The output ends of the reference light path 12 and the detection light path 13 are both connected with the detector 14. The reference light path 12 does not pass the developing reagent into the detector 14, only the baseline of the reaction reagent is identified. After the measured sample is mixed with the developing reagent, it enters the detection light path 13, and the detector 14 identifies the photoelectric signal of the reaction product. Finally, the photoelectric signal data of the detection cell 23 and the photoelectric signal data of the reference cell 22 are collected by the detector 14, and the final detection result is calculated and processed by the ratio method. After the two groups of data are collected, the ratio method is used to calculate as follows:

[0079]

[0080] Wherein: 、 The molar absorption coefficients of the primary and secondary wavelengths respectively, L is the optical path, and C is the concentration of the measured sample. By this method, the detection error caused by turbidity, color and other factors of the solution can be effectively removed.

[0081] As an embodiment, the shipborne flow analysis module 7 further includes a quantitative valve 24, and a mixing device I 25 for mixing the measured sample, the digestion liquid and the oxidizing agent uniformly is arranged between the quantitative valve 24 and the digestion treatment device 8. The input end of the quantitative valve 24 is connected with the peristaltic pump 15, the output end of the quantitative valve 24 is connected with the mixing device I 25, and the output end of the mixing device I 25 is connected with the digestion treatment device 8.

[0082] The peristaltic pump 15 drives the sample to be measured into the quantitative valve 24 and then into the mixer I 25, the peristaltic pump 15 drives the digestion solution into the mixer I 25 through the switching valve I 29 to mix with the sample to be measured, and the sample to be measured is adjusted by acid. The peristaltic pump 15 drives the oxidant into the mixer I 25 through the switching valve II 30 to mix with the sample to be measured adjusted by acid, and then the sample to be measured and the oxidant are mixed into the digestion treatment device 8.

[0083] As an embodiment, the shipborne flow analysis module 7 further comprises a mixer II 26, the input end of the mixer II 26 is connected with the peristaltic pump 15 and the cooling device 9 respectively, the output end of the mixer II 26 is connected with the reference cell 22, and the switching valve III 27 is further arranged between the mixer II 26 and the reference cell 22.

[0084] The sample to be measured after high-temperature digestion is cooled by the cooling device 9 and then enters the mixer II 26, the peristaltic pump 15 drives the reducing agent into the mixer II 26 to mix with the sample to be measured after high-temperature digestion, and then the reducing agent and the sample to be measured after high-temperature digestion enter the reference cell 22 through the switching valve III 27.

[0085] As an embodiment, the shipborne flow analysis module 7 further comprises a mixer III 28, the input end of the mixer III 28 is connected with the peristaltic pump 15 and the switching valve III 27 respectively, the output end of the mixer III 28 is connected with the color developing heating device 10, and the output end of the color developing heating device 10 is connected with the detection light path 13.

[0086] The switching valve III 27 is switched to connect the output end of the switching valve III 27 with the input end of the mixer III 28, the peristaltic pump 15 drives the color developing agent into the mixer III 28 to mix with the sample to be measured after digestion, and then the color developing agent and the sample to be measured after digestion enter the color developing heating device 10 to generate a stable blue compound.

[0087] The working principle of the cruise type total phosphorus automatic analyzer is as follows:

[0088] Initially, the injection device 17 is connected to the calibration chamber 5. After the standard sample is injected (i.e., the calibration solution is drawn) into the calibration tube 16, calibration is performed to obtain the standard sample curve. Then, the motor is started, causing the motor to drive the injection device 17 to move horizontally along the guide rail to the corresponding position, thereby connecting the injection device 17 to the sample cell 4, and thus achieving a sliding switch to water sample collection. The water sample to be tested is drawn to the quantitative valve 24 by the peristaltic pump 15. After quantification, the sample to be tested is pushed by the peristaltic pump 15 to mix evenly with the sulfuric acid digestion solution in the mixer I 25, which plays a role in automatically adjusting the acidity of the sample to be tested. The peristaltic pump 15 then drives the potassium permanganate solution (as an oxidant) into the mixer I 25 through the switching valve II 30 and mixes evenly with the acid-adjusted sample to be tested. Finally, they enter the digestion treatment device 8 for mixing and digestion. The digestion temperature is 120℃. The digestion time can be controlled by adjusting the reaction tube length of the digestion treatment device 8, thereby ensuring that the sample is fully digested and oxidized. After digestion, the sample is rapidly cooled to a low temperature by cooling device 9, and then enters mixer II 26. Peristaltic pump 15 drives ascorbic acid solution (as a reducing agent) into mixer II 26 and mixes it evenly with the cooled, high-temperature digested sample. Then, it enters reference cell 22 through switching valve III 27. After a period of reaction, the path is switched by switching valve III 27, connecting the output of switching valve III 27 to the input of mixer III 28. Peristaltic pump 15 drives ammonium molybdate colorimetric reagent into mixer III 28 and mixes it evenly with the digested sample. Then, they enter the colorimetric heating device 10 together to react and generate a stable blue compound. Colorimetric analysis is performed at a detection optical path 13 with a wavelength of 880 nm. By comparing the absorbance with that of reference cell 22 without the colorimetric reagent, interference caused by matrix color in the water sample can be eliminated. Phosphorus (as PO4) 3- The mass concentration of the reagent is directly proportional to its absorbance, and the entire testing process is controlled by a computer software workstation. All reagents are stored in reagent compartment 3 and drawn out by peristaltic pump 15 without manual addition. All chemical reactions are carried out under closed reaction conditions. The flow paths of sulfuric acid digestion solution and potassium permanganate oxidant are equipped with switching valve I 29 and switching valve II 30, respectively, which can switch between reagents and cleaning water. Automatic water cleaning is performed after the test to avoid the risk of corrosion caused by prolonged presence of acid and oxidant.

Claims

1. A cruise total phosphorus automatic analyzer characterized by, The application relates to a shipborne flow analysis device, which comprises the following parts: a slide switching sample injection module (1) which comprises a liquid storage chamber (2) and a reagent bin (3) for containing reaction reagents, the liquid storage chamber (2) comprises a sample pool (4) for storing samples to be measured and a calibration cavity (5) for storing standard samples, an injection device (6) is arranged above the liquid storage chamber (2) and moves back and forth along the horizontal direction and is connected with the sample pool (4) or the calibration cavity (5); a shipborne flow analysis module (7) which comprises a digestion treatment device (8) for heating and digesting the samples to be measured, a cooling device (9) which is connected with the digestion treatment device (8) through pipelines and is used for cooling the digested samples to be measured, and a color developing heating device (10) which is connected with the output end of the cooling device (9) through pipelines and is used for developing the color of the cooled samples to be measured; an optical detection module (11) which comprises a reference light path (12) for the flow of the samples to be measured which have not been added with a color developing agent and have been digested, a detection light path (13) for the flow of the samples to be measured which have been added with a color developing agent and have been digested, and a detector (14) for collecting the photoelectric signals of reaction products, and the output ends of the reference light path (12) and the detection light path (13) are connected with the detector (14); a peristaltic pump (15) for driving the samples to be measured and the reaction reagents to enter a flow path and react; wherein the slide switching sample injection module (1), the shipborne flow analysis module (7), the optical detection module (11) and the peristaltic pump (15) are connected through pipelines. A plurality of calibration tubes (16) for the flow of standard samples are arranged in the calibration cavity (5), and the number of the calibration tubes (16) is at least five. The injection device (6) comprises an injection device (17) which is connected with the liquid storage chamber (2) in a sliding mode, one end of the injection device (17) is connected with a driving assembly (18) for driving the injection device (17) to move back and forth along the horizontal direction, and the other end of the injection device (17) is connected with the peristaltic pump (15). The digestion treatment device (8) comprises a heater (19) for heating the samples to be measured, and an ultraviolet digestion tube (20) for light digestion of the samples to be measured is arranged on the outer side of the heater (19). A check valve (21) and a reference pool (22) for containing the digested samples to be measured without a color developing agent are sequentially arranged on the flow path of the reference light path (12), and the input end of the check valve (21) is connected with the peristaltic pump (15). A detection pool (23) for containing the digested samples to be measured with a color developing agent is arranged on the flow path of the detection light path (13), and the input end of the detection pool (23) is connected with the peristaltic pump (15).

2. The cruise type automatic total phosphorus analyzer according to claim 1, characterized in that, ​ 3. The cruise type automatic total phosphorus analyzer according to claim 1, characterized in that, ​ 4. The automatic analyzer for total phosphorus according to claim 1, wherein ​ 5. The cruise type automatic total phosphorus analyzer according to claim 1, characterized in that, ​ 6. The automatic analyzer for cruise total phosphorus according to claim 1, characterized in that, ​ 7. The automatic analyzer for cruise total phosphorus according to claim 1, characterized in that, The shipborne flow analysis module (7) further comprises a quantitative valve (24), a mixing device I (25) for mixing the sample to be measured, the digestion liquid and the oxidizing agent uniformly is arranged between the quantitative valve (24) and the digestion treatment device (8), the input end of the quantitative valve (24) is connected with the peristaltic pump (15), the output end of the quantitative valve (24) is connected with the mixing device I (25), and the output end of the mixing device I (25) is connected with the digestion treatment device (8).

8. The automatic analyzer for cruise total phosphorus according to claim 5, characterized in that, The shipborne flow analysis module (7) further comprises a mixing device II (26), the input end of the mixing device II (26) is connected with the peristaltic pump (15) and the cooling device (9) respectively, the output end of the mixing device II (26) is connected with the reference cell (22), and a switching valve III (27) is further arranged between the mixing device II (26) and the reference cell (22).

9. The automatic analyzer for cruise total phosphorus according to claim 8, characterized in that, The shipborne flow analysis module (7) further comprises a mixing device III (28), the input end of the mixing device III (28) is connected with the peristaltic pump (15) and the switching valve III (27) respectively, the output end of the mixing device III (28) is connected with the color developing heating device (10), and the output end of the color developing heating device (10) is connected with the detection light path (13).

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