CN107703321B - Automatic detecting analyzer for water quality of multiple pollutant components - Google Patents

Automatic detecting analyzer for water quality of multiple pollutant components Download PDF

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CN107703321B
CN107703321B CN201711149165.5A CN201711149165A CN107703321B CN 107703321 B CN107703321 B CN 107703321B CN 201711149165 A CN201711149165 A CN 201711149165A CN 107703321 B CN107703321 B CN 107703321B
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detection
detection components
subsets
components
water sample
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CN107703321A (en
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韩培良
张震
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SHANDONG JUN INTO ENVIRONMENTAL MONITORING Co.,Ltd.
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Shandong Jun Into Environmental Monitoring Co ltd
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N35/00Automatic analysis not limited to methods or materials provided for in any single one of groups G01N1/00 - G01N33/00; Handling materials therefor
    • G01N35/00584Control arrangements for automatic analysers
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Abstract

An automatic detecting analyzer for water quality with multiple pollutant components can be used for monitoring Chemical Oxygen Demand (COD), biochemical oxygen demand (BOD5) for five days, heavy metals (copper, mercury, arsenic, chromium, lead, zinc, antimony, nickel, etc.), total nitrogen, total phosphorus, etc. Wherein, through the volume of controller according to the water sample in the sample container to confirm the kind and the order of the reagent that conveys in the reaction vessel through the multi-ported valve, can reduce the requirement to detecting the water sample under the condition of guaranteeing to detect the precision.

Description

Automatic detecting analyzer for water quality of multiple pollutant components
Technical Field
The invention relates to an automatic analysis technology, in particular to a multi-component automatic water quality analyzer.
Background
The environmental problem is a problem of people who pay attention to the environment widely nowadays, and becomes a great problem in the current development of China, and the development of the world economy brings not only improvement of living conditions but also environmental pollution and destruction of environmental resources to human beings. Therefore, the method has important theoretical significance and practical significance for timely and accurately analyzing and monitoring the environmental pollutants and managing and planning the environment.
With the development of economic society, the scale of cities is continuously enlarged, the water consumption is continuously increased, and the waste water and sewage discharged into rivers, lakes and reservoirs are continuously increased. The quality of water affects both industrial and agricultural production and daily life of people, the quality of water resources in China continuously declines over the years, the water environment continuously worsens, water shortage and accidents caused by pollution continuously occur, not only is the factory stopped, the agricultural production is 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 the water quality problem is more and more concerned.
Accurate analysis and detection of various pollutant indexes are very necessary means for realizing total pollutant emission control and various environmental protection measures. Pollutants in water bodies contain, in addition to inorganic compounds, a large amount of organic matter that affects the ecosystem in the form of toxicity and reduction of dissolved oxygen in the water body.
The pollutants in the water body comprise organic pollutants and inorganic pollutants. Wherein, the organic pollutants can be divided into biodegradable organic pollutants and organic pollutants which are difficult to biodegrade; inorganic contaminants include heavy metals, inorganic salts, acids, bases, and the like. According to the surface water quality standard issued by China in years, a plurality of components need to be monitored, including: chemical oxygen demand (C0D), biochemical oxygen demand (BOD5), heavy metals (copper, mercury, arsenic, chromium, lead, zinc, antimony, nickel, etc.), total nitrogen, total phosphorus, etc.
The existing water quality monitoring methods comprise two methods: the first method is sampling on site and monitoring on line; the second is manual sampling, which is analyzed off-line by an analytical instrument. The online detection can be used for acquiring water quality data in real time and uninterruptedly, but has high requirements on field instruments and equipment, high investment cost and relatively low measurement accuracy, and can detect partial components and cannot detect the whole components. The off-line analysis has the characteristics of high measurement precision and comprehensive detection results, but the off-line analysis is non-real-time, needs to be carried back to a laboratory for detection after on-site sampling, and can be subjected to factors such as change or leakage in the transportation process, so that the detection of all detection components of a water sample in the laboratory is not enough.
In order to solve the above technical problems, a prior application proposes a multi-component automatic water quality analyzer, which determines the type and sequence of reagents transferred to a reaction container through a multi-way valve according to the volume of a water sample in a sample container through a controller, wherein, when the water sample is insufficient, for the mutually related detection components, the detection content of a subset is determined through the detection result of a master set, so that the water sample used for detection can be reduced.
Disclosure of Invention
The invention provides an improved automatic water quality analysis instrument for components, which can further reduce the use of a detection water sample when associated detection components exist.
As an aspect of the present invention, there is provided an automatic water quality detecting analyzer comprising: the device comprises a sample container, a peristaltic pump, a multi-way valve, a reaction container, a reagent container, a detection device and a controller; the sample container and the reagent container are respectively communicated with an inlet pipeline of the multi-way valve, and the reaction container is communicated with an outlet pipeline of the multi-way valve; the peristaltic pump is opened and closed according to a valve of the multi-way valve, and pumps the water sample in the sample container and the reagent in the reagent container to the reaction container; the detection device is arranged in the reaction container and is used for detecting the content of the component to be detected in the sample; the device also comprises a diluent bottle communicated with the inlet of the multi-way valve; and when the volume of the water sample in the sample is lower than the volume required by all the detection components, the controller determines the correlated detection components in the detection components, and determines whether to perform detection after dilution on the subset according to the detection result of the mother set in the correlated detection components.
Preferably, if the detection result of the mother set in the correlated detection components is greater than a threshold value, at least one of the subset is detected, and at least one of the subset is not detected; and if the detection result of the parent set in the correlated detection components is smaller than a threshold value, not detecting all the subsets.
Preferably, the diluent is pure water.
Preferably, if the detection result of the parent set of the correlated detection components is smaller than the threshold of all the subsets, no detection is performed on all the subsets.
Preferably, if the detection result of the mother set in the correlated detection components is greater than the threshold value of only one subset, only the subset is detected; when the subset is detected, the water sample for detecting the subset is diluted and then the subset is detected.
Preferably, the dilution factor is ρ12Where ρ is1Is the detection result of the mother set, p2Is the threshold for that subset.
Preferably, if the detection result of the parent set in the correlated detection components is only greater than the threshold value of a plurality of subsets, only the plurality of subsets are sequentially detected; when the plurality of subsets are detected, the water samples detected by each subset in the plurality of subsets are diluted and then the subset is detected.
Preferably, the diluent isThe release multiple is rho1iWhere ρ is1Is the detection result of the mother set, piThreshold for the ith subset.
Preferably, the kit further comprises a storage part, wherein the storage part stores minimum water samples required by different detection components.
Preferably, the storage unit stores mutual interference information between different detection components in a storage table.
Preferably, the storage unit further stores association information between the different detection components, the association information indicating an aggregate relationship between the detection components.
Preferably, after the controller determines the components to be detected, whether the volume of the water sample in the sample container is larger than the required volume of the water sample is judged according to the data of the storage part; if the volume of the water sample is smaller than the required volume of the water sample, the controller matches all detection components according to the data of the storage part and judges whether non-interfering detection components exist or not, and if the non-interfering detection components exist, the controller detects the non-interfering detection components sequentially when determining the detection components; wherein, after detecting one of the non-interfering detection components, the detected waste liquid is not discharged to the waste liquid pool, and the other one of the non-interfering detection components is continuously detected by pumping the other detection reagent of the non-interfering detection components into the reaction container.
Drawings
Fig. 1 is a block diagram of the water quality automatic detection analyzer according to the embodiment of the present invention.
Fig. 2 is a flow chart of the detection steps of the automatic water quality detection analyzer according to the embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the technical solutions of the present invention, the present invention will be briefly described below by using embodiments, and it is obvious that the following description is only one embodiment of the present invention, and for those skilled in the art, other technical solutions can be obtained according to the embodiments without inventive labor, and also fall within the disclosure of the present invention.
The water quality automatic detection analyzer of the embodiment of the invention is used for analyzing the content of various pollutants in a water sample offline, and comprises a sample container 10, a peristaltic pump 20, a multi-way valve 30, a reaction container 40, a plurality of groups of reagent containers 50, a detection device 60, a controller 70, a storage part 80 and a diluent bottle 90, wherein the peristaltic pump 20, the multi-way valve 30, the reaction container 40, the plurality of groups of reagent containers 50, the detection device 60, the controller 70 and the.
The sample container 10 is used for receiving water samples sampled and transported to a detection laboratory on site, and is provided with a volume sensing element capable of detecting the volume of the water samples in the sample container 10. The reagent container sets 50 of the reagent container sets may include a buffer, a sensitizer and a developer, the developer may use a 1- (2-pyridylazo) -2-naphthol (PAN) solution, the sensitizer may use a cetylpyridinium bromide (CPB) solution, and the buffer may use an acetic acid-sodium acetate buffer solution, which are measured by spectrophotometry, for example, for the detection of copper ions.
The multi-way valve 30 is controlled by the controller 70 to select different channels for sampling water and for sampling and discharging reagents. The inlet channels of the multi-way valve 30 are respectively communicated with the sample container 10 and the reagent container 50, and the outlet pipelines of the multi-way valve 30 are communicated with the reaction container 40. The peristaltic pump 20 pumps the water sample in the sample container and the reagent in the reagent container to the reaction container 40 according to the valve opening and closing of the multi-way valve. The peristaltic pump 20 includes a roller driven by a stepping motor, the roller is disposed outside the tube, and the stepping motor drives the roller to rotate and pump the reagent or the sample.
The reaction container 40 receives a water sample and a reagent, and the content of a detection component in the water sample is measured by the detection device 60 in the reaction container. The detection device 60 may include various detectors, such as a spectrophotometer, for colorimetrically determining the content of heavy metal ions in the water sample, and a near infrared spectrometer for determining the Chemical Oxygen Demand (COD) in the water sample by near infrared spectroscopy, for example.
The memory section 80 stores the minimum water sample required for different detection components, which can be determined by the precision of the test equipment and the parameter requirements, for example, 20ml for spectrophotometric detection of the minimum water sample of copper ions. The storage part 80 also stores mutual interference information among different detection components, such as COD value in a water sample, which is actually measured by near infrared spectroscopy without adding reagent, so that the detection of COD does not cause interference to the spectrophotometric detection of heavy ions, and the COD detection is determined as the non-interference detection of the detection of heavy metal ions; for example, detection of nitrate and copper ions does not interfere with each other.
The diluent bottle 90 contains a diluent therein which communicates with an inlet of the multi-way valve 30. The diluent bottle 90 may be one or more, and the diluent in the diluent bottle 90 may be pure water or a buffer. The controller 70 determines whether to use the dilution liquid bottle 90 for diluting the sampled water introduced into the multi-way valve 30, based on the volume of the sampled water in the sample container 10 and the detection result of the detection device 60.
The water quality automatic detection analyzer also comprises an input device, and a user can input detection components needing to be detected through the input device. After the controller 70 receives the components to be detected, calculating the required water samples of all the detected components; judging whether the volume of the water sample in the sample container 10 is larger than the required water sample volume according to the data of the storage part 80; if the volume of the water sample is larger than the required volume, the controller 70 carries out detection according to the detection component sequence input by the user; if the volume of the water sample is smaller than the required volume of the water sample, the controller 70 matches all detection components according to the data of the storage part 80 to judge whether non-interfering detection components exist, and if the non-interfering detection components exist, the controller 70 detects the non-interfering detection components sequentially when determining the detection components; after one of the non-interfering detection components is detected, the detected waste liquid is not discharged to the waste liquid pool, and the other one of the non-interfering detection components is continuously detected by pumping the other detection reagent into the reaction container 10. For example, in the detection of the presence of COD and the content of copper ions in the detected components, the controller 70 firstly conveys the water sample into the reaction container 40 through the peristaltic pump 20, and determines the COD value of the water sample through the near infrared spectrum; then, instead of discharging the detected water sample to the waste liquid pool, the controller 70 pumps the copper ion detection reagent to the reaction container 40 through the peristaltic pump 20, and determines the copper ion content in the water sample through the spectrophotometer.
Preferably, the automatic water quality detecting analyzer of the present invention further includes a flow meter that measures the volume of the reagent that reaches the reaction vessel, and corrects the detection result of the other of the non-interfering detection components based on the measured volume of the reagent that is added at the time of detection of the non-interfering detection components when the other of the non-interfering detection components is detected.
The storage section 80 also stores association information between different detection components. The association information indicates a set relationship between the detection components. For example, the collective relationship between free antimony content, antimony 3 valent content, and antimony 5 valent content, where free antimony content is the parent set, antimony 3 valent content and antimony 5 valent content are the subset, and antimony 3 valent content and antimony 5 valent content are the complete set of free antimony content.
After the controller 70 determines that the detection of the mutually interfering components is complete, the volume of the water sample in the sample container is still less than the required water sample volume; the controller 70 determines the correlated detection components among the detection components from the data stored in the storage unit 80, and determines whether or not to detect the subset from the detection result of the parent set among the correlated detection components. Specifically, if the detection result of the mother set in the correlated detection components is greater than a threshold, at least one of the subset is detected, and at least one of the subset is not detected; and if the detection result of the parent set in the correlated detection components is smaller than a threshold value, not detecting all the subsets. When the subset is detected, the subset is detected after the water sample for detecting the subset is diluted. Preferably, the dilution factor is ρ12Where ρ is1Is the detection result of the mother set, p2Is the threshold for that subset.
For example, the inputted detection components include free antimony content, antimony value 3 and antimony value 5, the controller 70 first controls the automatic water quality detection analyzer to detect the free antimony content, if it detects itIf the detection result is less than the minimum safety threshold value in the chromium (3) content and the antimony (5) content, the chromium (3) content and the antimony (5) content are not measured, and only the upper detection limit less than the free antimony content is given when the result is displayed; and if the detection result is greater than the threshold value of one of the chromium (III) content of 3 valence and the antimony (Sb) content of 5 valence, measuring the chromium (III) content of 3 valence or the antimony (Sb) content of 5 valence, determining the content of one of the chromium (III) content and the antimony (Sb) content of 5 valence, and determining the content of the other one of the chromium (III) content and the antimony (Sb). And when the content of the chromium with a valence of 3 or the content of the antimony with a valence of 5 is measured, diluting a detection water sample and detecting, wherein the dilution multiple is rho12Where ρ is1Is the detection result of the mother set, p2Is the threshold for that subset.
The automatic detection method of the water quality automatic detection analyzer in the embodiment of the invention is shown in figure 2 and comprises the following steps: (1) putting the water sample into a sample container, and determining the volume of the water sample; (2) inputting detection components, and determining the volumes required by all the detection components; (3) judging whether the volume of the water sample in the sample container is larger than the required water sample volume; if the volume of the water sample is larger than the required volume, entering the step (4), and otherwise, entering the step (5); (4) detecting according to the sequence of the detection components input by the user; (5) sequentially detecting the detection components which do not interfere with each other; (6) determining whether to dilute and detect the detection water sample for the subset according to the detection result of the mother set in the mutually associated detection components; if the detection result of the parent set in the correlated detection components is smaller than the threshold of all the subsets, entering the step (7); if the detection result of the mother set in the correlated detection components is larger than the threshold value of only one subset, entering the step (8); if the detection result of the parent set in the correlated detection components is only larger than the threshold values of a plurality of subsets, entering the step (9); (7) no detection is performed on all subsets; (8) diluting the water sample for detecting the subset and then detecting the subset; (9) sequentially detecting the plurality of subsets, and when detecting the plurality of subsets, diluting the water sample for detecting each subset in the plurality of subsets and then detecting the subset; (10) the detection is performed in sequence, i.e., not belonging to the non-interfering detection components nor to the non-associated detection components.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and are intended to be within the scope of the invention.

Claims (1)

1. An automatic water quality detection analyzer, comprising: a sample container, a peristaltic pump, a multi-way valve, a reaction container, a reagent container, a detection device, a storage part and a controller; the sample container and the reagent container are respectively communicated with an inlet pipeline of the multi-way valve, and the reaction container is communicated with an outlet pipeline of the multi-way valve; the peristaltic pump is opened and closed according to a valve of the multi-way valve, and pumps the water sample in the sample container and the reagent in the reagent container to the reaction container; the detection device is arranged in the reaction container and is used for detecting the content of the component to be detected in the sample; the storage unit stores association information between different detection components, the association information indicating a set relationship between the detection components; the storage part also stores mutual interference information among different detection components; the method is characterized in that: the device also comprises a diluent bottle communicated with the inlet of the multi-way valve, and diluent is contained in the diluent bottle; after the controller determines the components to be detected, judging whether the volume of the water sample in the sample container is larger than the required water sample volume according to the data of the storage part; if the volume of the water sample is smaller than the required volume of the water sample, the controller matches all detection components according to the data of the storage part and judges whether non-interfering detection components exist or not, and if the non-interfering detection components exist, the controller detects the non-interfering detection components sequentially when determining the detection components; then, the controller determines the mutually associated detection components in the detection components, and determines whether to perform detection after dilution on the detection water sample for the subset according to the detection result of the mother set in the mutually associated detection components; wherein, if said each otherIf the detection result of the mother set in the associated detection components is greater than the threshold value, detecting at least one of the subsets, and not detecting at least one of the subsets; if the detection result of the mother set in the mutually related detection components is smaller than a threshold value, all the subsets are not detected; if the detection result of the mother set in the mutually related detection components is smaller than the threshold value of all the subsets, all the subsets are not detected; if the detection result of the parent set in the mutually related detection components is only larger than the threshold values of a plurality of subsets, only sequentially detecting the plurality of subsets; when the plurality of subsets are detected, diluting the water sample for detection of each subset in the plurality of subsets, and then detecting the subset, wherein the dilution multiple is rho1iWhere ρ is1Is the detection result of the mother set, piThreshold for the ith subset.
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CN107525905A (en) * 2017-09-19 2017-12-29 苏州奥特福环境科技有限公司 A kind of sewage detection device
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CN101819212B (en) * 2010-04-15 2013-04-24 马三剑 On-line automatic monitoring device for water quality mercury
CN102288600A (en) * 2011-05-13 2011-12-21 重庆大学 Colorimetric measuring method for simultaneously measuring hexavalent chromium and lead
CN102495222B (en) * 2011-12-14 2013-10-30 力合科技(湖南)股份有限公司 Online stibium analyzer and method for detecting concentration of stibium of different forms in water sample
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