CN108760664B - Water quality multi-parameter automatic detection and analysis method - Google Patents
Water quality multi-parameter automatic detection and analysis method Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 238000001514 detection method Methods 0.000 title claims abstract description 114
- 238000004458 analytical method Methods 0.000 title claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 100
- 239000000126 substance Substances 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 230000000875 corresponding effect Effects 0.000 description 24
- 238000000034 method Methods 0.000 description 11
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 239000010865 sewage Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000003911 water pollution Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012372 quality testing Methods 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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Abstract
A multi-parameter automatic detection and analysis method for water quality is used for detecting various water quality parameters such as Chemical Oxygen Demand (COD), total phosphorus, ammonia nitrogen, phosphate or heavy metal content and the like, and comprises the following steps: (1) storing the influence parameters and threshold values of the water quality detection parameters; (2) dividing a water sample into a first detection water sample and a second detection water sample; (3) detecting a plurality of water quality parameters of a first detected water sample through a plurality of sensors of a detection device; (4) determining whether a second detected water sample is stored in a specific storage group or not according to the detection result of the first detected water sample and the information of all stored water samples; (5) and when the storage quantity of the second detected water samples in the specific storage group reaches a quantity threshold value, calibrating the sensor parameters corresponding to the specific storage group.
Description
Technical Field
The invention relates to the technical field of automatic analysis, in particular to an automatic detection and analysis method for multi-parameter detection of water quality.
Background
Water resources are important resources which depend on survival and development of human beings, and water resource environmental pollution can seriously affect the healthy living standard of local residents to cause chain damage of an ecological environment system, so that the protection of the water resources becomes a global environmental problem which is commonly concerned and increasingly emphasized by countries in the world.
With the rapid development of social economy and the acceleration of the urbanization and industrialization process, a large amount of urban domestic sewage and industrial wastewater is discharged into rivers, lakes and reservoirs, so that the problems of serious pollution of surface water and underground water and water pollution are increasingly prominent, and daily water and domestic water of people face serious threats and challenges. The quality of water resources is continuously reduced, the water environment is continuously deteriorated, water shortage and accidents caused by pollution are continuously caused, not only is the factory stopped, the agriculture reduced, even the ecological environment is extremely damaged, but also the sustainable development of the society is seriously threatened and the survival of human beings is seriously threatened, so that the water quality problem is more and more concerned.
The water quality monitoring takes environmental water bodies such as rivers, lakes, reservoirs, oceans, underground water and the like and water pollution sources such as domestic sewage, industrial wastewater, hospital sewage and the like as detection objects, and the water bodies are qualitatively analyzed and quantitatively analyzed by a specific detection method (such as a chemical method, an electrochemical method, an atomic absorption spectrophotometry, an ion chromatography, a gas chromatography and the like) to distinguish the types of pollutants in the water bodies and the concentrations of the pollutants, so that the water bodies are evaluated. The water quality detecting instrument is necessary equipment for providing timely, accurate and comprehensive scientific basis for water pollution monitoring and treatment, is an important premise and basis for formulating feasible pollution prevention and control plans and water resource environment protection, and has extremely important scientific significance for the safety monitoring and protection of the water resource environment.
In the automatic water quality detection analyzer, the sensor state is changed due to the influence of factors such as the working environment change of the sensor, the sensor is required to be calibrated according to the system parameters of the sensor by using standard solution in a certain time period, however, the calibration can be carried out only after a period of time, the standard solution is required to be prepared or purchased, the preparation requires manual participation, the process is complex, the storage life is short, the preparation needs to be carried out again after expiration, the calibration time of the automatic water quality detection analyzer is long, time and energy are consumed, and the automatic water quality detection analyzer is not beneficial to use of a user.
In order to solve the problems, the prior application provides an improved automatic water quality detection analyzer, which can calibrate parameters of a sensor in real time by storing part of water samples for calibration and does not need to prepare standard solution, thereby reducing the workload of manual participation, reducing the cost and improving the automation degree of a system. However, the existing water body usually contains pollutants with multiple components, the pollutant components are correlated, and specific pollutant components can interfere with the detection of other pollutant components, for example, when the turbidity in the water body is too large, the accuracy of the COD value detected by the ultraviolet absorbance method is too high, and the error of the detected COD value is too large, and if the water sample is stored and then used for the calibration of an ultraviolet spectrometer, the deviation of the calibration result is large.
Disclosure of Invention
The invention provides a further improved automatic multi-parameter detection and analysis method for water quality, which can avoid a water sample with large detection error as a calibration water sample, thereby reducing the calibration error and improving the accuracy of a detection result.
The invention provides a water quality multi-parameter automatic detection and analysis method, which comprises the following steps: (1) storing the influence parameters and threshold values of the water quality detection parameters; (2) inputting a water sample from a water body, and dividing the water sample into a first detection water sample and a second detection water sample; (3) detecting a plurality of water quality parameters of a first detected water sample through a plurality of sensors of a detection device; (4) determining whether a second detected water sample is stored in a specific storage group or not according to the detection result of the first detected water sample and the information of all stored water samples; (5) and when the storage quantity of the second detected water samples in the specific storage group reaches a quantity threshold value, calibrating the sensor parameters corresponding to the specific storage group.
Preferably, the step (4) comprises the following steps: (4.1) determining the measured value of the influence parameter of the water quality detection parameter corresponding to the specific storage group, comparing the measured value with the threshold value of the influence parameter, and if the measured values of all the influence parameters are smaller than the threshold value of the influence parameter, comparing the detection result of the water quality detection parameter corresponding to the specific storage group of the first detected water sample with the detection result of the water quality detection parameter corresponding to all the water samples of the specific storage group; (4.2) if the absolute value of the difference between the detection result of the water quality detection parameter corresponding to the specific storage group of the first detected water sample and the detection results of all the water samples in the specific storage group is greater than a first detection threshold, storing a second detected water sample corresponding to the first detected water sample into the specific storage group of the water sample storage part; (4.3) if the second detected water sample is stored in the specific storage group of the water sample storage part, recording the detection result and the storage time of the corresponding water quality detection parameter of the specific storage group of the second detected water sample.
Preferably, in the step (5), the quantity threshold value may be determined according to the number required for sensor parameter calibration.
Preferably, in the step (5), the number threshold may be set to 3 to 10, for example.
Preferably, the method further comprises the step (6) of discharging the stored water samples from the specific storage group when the storage time of the stored water samples in the specific storage group exceeds a time threshold.
Preferably, the threshold of the influence parameter is determined according to the degree of influence of the influence parameter on the detection result of the water quality detection parameter.
Preferably, the threshold of the impact parameter is set to be greater than 1% of the detection error of the water quality detection parameter when the impact parameter is greater than the threshold.
Preferably, the detection parameters include PH, turbidity, Chemical Oxygen Demand (COD), total phosphorus, ammonia nitrogen, phosphate or heavy metal content, etc.
Preferably, the sensor parameter is a standard curve of a sensor detection value and a measurement parameter.
Drawings
FIG. 1 is a flow chart of a water quality multi-parameter automatic detection and analysis method according to an embodiment of the present invention.
Fig. 2 is a schematic view of a system structure of the water quality multi-parameter automatic analyzer according to the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the multi-parameter automatic detection and analysis method for water quality of the embodiment of the invention, the detected water quality parameters can include various water quality parameters such as pH value, turbidity, Chemical Oxygen Demand (COD), total phosphorus, ammonia nitrogen, phosphate or heavy metal content, and the like, and referring to FIG. 1, the method comprises the following steps: (1) storing the influence parameters and threshold values of the water quality detection parameters; (2) inputting a water sample from a water body, and dividing the water sample into a first detection water sample and a second detection water sample; (3) detecting a plurality of water quality parameters of a first detected water sample through a plurality of sensors of a detection device; (4) determining whether a second detected water sample is stored in a specific storage group or not according to the detection result of the first detected water sample and the information of all stored water samples; (4.1) determining the measured value of the influence parameter of the water quality detection parameter corresponding to the specific storage group, comparing the measured value with the threshold value of the influence parameter, and if the measured values of all the influence parameters are smaller than the threshold value of the influence parameter, comparing the detection result of the water quality detection parameter corresponding to the specific storage group of the first detected water sample with the detection result of the water quality detection parameter corresponding to all the water samples of the specific storage group; (4.2) if the absolute value of the difference between the detection result of the water quality detection parameter corresponding to the specific storage group of the first detected water sample and the detection results of all the water samples in the specific storage group is greater than a first detection threshold, storing a second detected water sample corresponding to the first detected water sample into the specific storage group of the water sample storage part; (4.3) if the second detected water sample is stored in a specific storage group of the water sample storage part, recording the detection result and the storage time of the water quality detection parameters corresponding to the specific storage group of the second detected water sample; (5) when the storage quantity of the second detected water samples in the specific storage group reaches a quantity threshold value, calibrating sensor parameters corresponding to the specific storage group; (6) and when the storage time of the stored water samples in the specific storage group exceeds a time threshold, discharging the stored water samples from the specific storage group.
Referring to fig. 2, the automatic water quality testing analyzer for the automatic multi-parameter water quality testing and analyzing method according to the embodiment of the present invention includes an input unit 10, a water sample storage unit 20, a reagent container 30, a multi-way valve 40, a peristaltic pump 50, a reaction container 60, a storage unit 70, a control unit 80, and a calibration unit 90.
Specifically, in the method for multi-parameter automatic detection and analysis of water quality according to the embodiment of the present invention, in step (1), the storage unit 70 stores the influence parameters of each water quality detection parameter and the threshold thereof, for example, for the COD value detected by the ultraviolet absorbance method, when the turbidity value in the water sample is large or the PH value is greater than 10, the error of the detection value of the COD value is large; therefore, the parameters affecting the COD value in the storage portion are turbidity and PH, and the threshold values thereof can be predetermined by the standard sample, for example, the threshold values can be set such that when the turbidity and the PH are greater than the threshold values thereof, the COD value is detected with an error greater than 1%.
In the step (2), a water sample is input into the input unit 10 from the water body, and the water sample is divided into a first detection water sample and a second detection water sample. The detection water body can be environmental water bodies such as rivers, lakes, reservoirs, oceans, underground water and the like, can also be water pollution sources such as domestic sewage, industrial wastewater, hospital sewage and the like, and can also be water production sources such as water works, purified water plants and the like. The input water sample is larger than the detection sample amount required by detection, preferably, the input water sample is larger than two times or more than two times of the detection sample amount required by detection. The input part 10 includes a first container 11 and a second container 12, which divide an input water sample into two parts, the first container 11 storing a first detected water sample; the second container 12 stores a second detected water sample; the first detection water sample is used for determining a water body pollutant concentration value. The second detected water sample in the second container 12 can be stored in a specific storage group of the water sample storage unit 70, and used for calibration of the sensor parameters corresponding to the specific storage group.
In the step (3), the reagent in the reagent container 30 and the first detected water sample in the first container 11 are delivered to the reaction container 60 through the multi-way valve 40 and the peristaltic pump 50, and the plurality of water quality parameters of the first detected water sample are detected by the detection device 61 of the reaction container 60. Detection device 61 includes multi-parameter detection device, and the quality of water parameter that its detected can be PH value, turbidity, Chemical Oxygen Demand (COD), total phosphorus, ammonia nitrogen, phosphate or heavy metal content etc. can use the sensor to the quality of water parameter setting detection device 61 that needs detected, for example can use the PH value detector to detect the PH value, uses the turbidity of turbidity appearance monitoring water quality, uses ultraviolet spectrometer to detect chemical oxygen demand.
In the step (4), it is determined whether to store the second detected water sample in the specific storage group of the water sample storage unit 20 according to the detection result of the first detected water sample and all the water sample information stored in the storage unit 70. Specifically, the method comprises the following steps: (4.1) the control part 80 determines the measured value of the influence parameter of the water quality detection parameter corresponding to the specific storage group, compares the measured value with the threshold value, and if the measured values of all the influence parameters are smaller than the threshold value, compares the detection result of the water quality detection parameter corresponding to the specific storage group of the first detected water sample with the detection result of the detection parameter corresponding to all the water samples of the specific storage group; (4.2) if the absolute value of the difference between the detection result of the water quality detection parameter corresponding to the specific storage group of the first detected water sample and the detection results of all the water samples in the specific storage group is greater than a first detection threshold, storing a second detected water sample corresponding to the first detected water sample into the specific storage group of the water sample storage part; (4.3) if the second detected water sample is stored in the specific storage group of the water sample storage part, recording the detection result and the storage time of the corresponding water quality detection parameter of the specific storage group of the second detected water sample. For example, when determining whether to store the second detected water sample in the COD calibration group of the water sample storage unit 20, the control unit 80 determines the influence parameters of the COD value as turbidity and PH value through the information of the storage unit 70, compares the turbidity and PH value of the first detected water sample with the threshold values thereof, if both the turbidity and the PH value are smaller than the threshold values thereof, the control unit 80 compares the COD value of the first detected water sample with the COD values of all the stored water samples of the COD calibration group in the water sample storage unit 20, and if the absolute value of the difference between the COD value of the first detected water sample and the COD values of all the stored water samples of the COD calibration group in the water sample storage unit 20 is greater than the first detection threshold value, stores the second detected water sample corresponding to the first detected water sample in the COD calibration group of the water sample storage unit 20. The first detection threshold may be preset, for example, may be set to 1/10 for the sensor's range.
In step (5), when the storage quantity of the second detected water samples in the storage group of the water sample storage unit 20 reaches the quantity threshold, the calibration unit 90 calibrates the sensor parameter corresponding to the specific storage group. The quantity threshold value can be determined according to the quantity required by sensor parameter calibration, and can be set to be 3-10 for example. For example, for calibration of a relationship curve between a sensor detection value and a pollutant content, the quantity threshold is set to 5, when 5 COD group water samples in the water sample storage unit 20 are obtained, the water samples in the water sample storage unit 20 are sequentially input into the reaction container 60, a measurement value of the water sample is detected by the ultraviolet spectrometer of the detection device 61, and the measurement value is fitted with a detection result of the water sample in the storage unit 20, so as to determine a standard relationship curve of the ultraviolet spectrometer of the detection device 61.
And (6) when the storage time of the stored water samples in the specific storage group exceeds a time threshold, discharging the stored water samples from the specific storage group. Since the sample has a certain storage life, the controller 80 may monitor the storage time of the water sample in the water sample storage unit 20 according to the data of the storage unit 70, and when the storage time of the specific water sample is greater than the time threshold, the specific water sample is discharged through the waste liquid channel, thereby ensuring the quality of the sample for sensor calibration. The time threshold may be, for example, 7 days, 15 days, 30 days, etc.
In the system embodiment, each included module or unit is only divided according to functional logic, but is not limited to the above division as long as the corresponding function can be realized; in addition, the specific names of the functional modules are only for convenience of distinguishing from each other and are not used for limiting the protection scope of the present invention.
The above examples are merely representative of preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (4)
1. A multi-parameter automatic detection and analysis method for water quality comprises the following steps: (1) storing the influence parameters and threshold values of the water quality detection parameters; (2) inputting a water sample from a water body, and dividing the water sample into a first detection water sample and a second detection water sample; (3) detecting a plurality of water quality parameters of a first detected water sample through a plurality of sensors of a detection device; (4) determining whether a second detected water sample is stored in a specific storage group or not according to the detection result of the first detected water sample and the information of all stored water samples; wherein, step (4) includes: (4.1) determining the measured value of the influence parameter of the water quality detection parameter corresponding to the specific storage group, comparing the measured value with the threshold value of the influence parameter, and if the measured values of all the influence parameters are smaller than the threshold value of the influence parameter, comparing the detection result of the water quality detection parameter corresponding to the specific storage group of the first detected water sample with the detection result of the water quality detection parameter corresponding to all the water samples of the specific storage group; (4.2) if the absolute value of the difference between the detection result of the water quality detection parameter corresponding to the specific storage group of the first detected water sample and the detection results of all the water samples in the specific storage group is greater than a first detection threshold, storing a second detected water sample corresponding to the first detected water sample into the specific storage group of the water sample storage part; (4.3) if the second detected water sample is stored in a specific storage group of the water sample storage part, recording the detection result and the storage time of the water quality detection parameters corresponding to the specific storage group of the second detected water sample; (5) when the storage quantity of the second detected water samples in the specific storage group reaches a quantity threshold value, calibrating sensor parameters corresponding to the specific storage group; (6) and when the storage time of the stored water samples in the specific storage group exceeds a time threshold, discharging the stored water samples from the specific storage group.
2. The automatic detection and analysis method for multiple parameters of water quality according to claim 1, characterized in that: the detection parameters include pH value, turbidity, Chemical Oxygen Demand (COD), total phosphorus, ammonia nitrogen, phosphate or heavy metal content.
3. The automatic detection and analysis method for multiple parameters of water quality according to claim 2, characterized in that: in the step (5), the quantity threshold is determined according to the quantity required by sensor parameter calibration.
4. The automatic detection and analysis method for multiple parameters of water quality according to claim 3, characterized in that: in the step (5), the number threshold is set to be 3-10.
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