Detection method of free residual chlorine in water, control device, storage medium and system

Abstract

The embodiment of the invention provides a method for detecting free residual chlorine in water, a control device, a storage medium and a system, and belongs to the technical field of free residual chlorine detection. The detection method performs detection based on a discontinuous chemical analyzer, the discontinuous chemical analyzer comprises a sample position, a reagent position and a cuvette position, and the detection method comprises the following steps: constructing a detection work list comprising related information of a plurality of water samples to be detected, the related information of each to-be-detected water sample comprises the following information: a water sample number, a sample position of the water sample, and a reagent position of a detection reagent corresponding to the water sample; and controlling each to-be-detected water sample in the detection work list and the corresponding detection reagent to carry out chemical reaction in the cuvette position so as to carry out free residual chlorine detection on each to-be-detected water sample in the detection work list. And the free residual chlorine in the water sample in the detection work list can be automatically, efficiently, quickly and accurately detected.

Description

Technical Field

[0001] The present invention relates to the technical field of free residual chlorine detection, and in particular to a detection method, a control device, a storage medium and a system for free residual chlorine in water. Background Art

[0002] In water treatment processes used in oil refining and chemical enterprises, power plants, domestic water fields, etc., sodium hypochlorite, chlorine, chlorine-free and other agents need to be added to the water for sterilization and algae removal. Therefore, it is generally required that a certain amount of free residual chlorine remain in the water so that it can continue to play a sterilization role. Therefore, a large number of water samples need to be tested for free residual chlorine in the water. Most water quality testing laboratories carry out free residual chlorine testing. The principle of the determination is: under the condition of pH 6.2-6.6, aminodiethylaniline sulfate (DPD) reacts with the free residual chlorine in the water sample to generate a red semiquinone compound. The color depth of the red semiquinone compound is proportional to the residual chlorine content. The color of the red semiquinone compound can be determined by spectrophotometry.

[0003] At present, the more advanced laboratory free residual chlorine detection technology is to use DPD powder pillow reagent and residual chlorine rapid tester (for example, a small single-parameter spectrophotometer) for manual detection, including: 1) clean the sample bottle, and replace the sample bottle with the water sample to be tested 2-3 times, take a certain amount (for example, 10ml) of water sample into the sample bottle, put it into the instrument, cover it with a light-shielding cover, and first "return to zero" to eliminate background interference such as turbidity and color in the water sample; 2) use scissors to cut open a pack of solid DPD reagent powder pillow, carefully pour it into the sample bottle, shake it well and color it for 1 minute, put it into the colorimetric slot of the residual chlorine rapid tester, cover it with a light-shielding cover, and read the colorimetric reading; 3) clean the sample bottle after the determination is completed.

[0004] The above-mentioned determination method using DPD powder pillow reagent and residual chlorine rapid tester has the following disadvantages: 1) manual determination is inefficient; 2) the color development time of 1 minute is not easy to control in the specific experimental process, but the color development time has a significant impact on the results. Each time a powder pillow is cut open, the amount of solid powder poured out is inconsistent. In addition, if the solid powder cannot be completely dissolved, it may lead to inadequate reaction, etc., resulting in less than ideal precision and accuracy of the determination method data; 3) the price of each package of solid DPD reagent is relatively high for laboratory analysis. Summary of the invention

[0005] The purpose of the embodiment of the present invention is to provide a method for detecting free residual chlorine in water, which can realize automatic detection of free residual chlorine in water.

[0006] In order to achieve the above-mentioned purpose, an embodiment of the present invention provides a method for detecting free residual chlorine in water, which is based on an intermittent chemical analyzer for detection. The intermittent chemical analyzer includes a sample position, a reagent position, and a cuvette position. The method for detecting free residual chlorine in water includes: constructing a detection work list including relevant information of multiple water samples to be detected, wherein the relevant information of each water sample to be detected includes information about the following: the water sample number, the sample position where the water sample is located, and the reagent position where the detection reagent corresponding to the water sample is located; and controlling each water sample to be detected in the detection work list and the corresponding detection reagent to undergo a chemical reaction in the cuvette position to perform free residual chlorine detection on each water sample to be detected in the detection work list.

[0007] Optionally, before constructing the detection work list including relevant information of multiple water samples to be detected, the method for detecting free residual chlorine in water also includes: diluting a residual chlorine standard solution of a preset concentration into a group of residual chlorine solutions through the intermittent chemical analyzer, each residual chlorine solution in the group of residual chlorine solutions corresponding to a concentration; controlling the group of residual chlorine solutions to undergo a chemical reaction with a detection reagent of the same specification in the cuvette position, the detection reagent of the same specification having the same concentration and the same dosage; for each residual chlorine solution in the group of residual chlorine solutions, after the chemical reaction is completed, reading the corresponding standard absorbance value; and drawing a free residual chlorine standard curve based on the standard absorbance value and the corresponding concentration of each residual chlorine solution.

[0008] Optionally, the free residual chlorine detection for each water sample to be detected in the detection work list includes: determining the absorbance value of the corresponding chemical reaction result for each water sample to be detected; and determining the free residual chlorine concentration of the water sample to be detected based on the absorbance value of the chemical reaction result and the free residual chlorine standard curve.

[0009] Optionally, determining the absorbance value of the corresponding chemical reaction result includes: before conducting a chemical reaction, reading a first absorbance value of the water sample to be tested; after the chemical reaction is completed, reading a second absorbance value of the corresponding post-reaction solution; and determining the difference between the second absorbance value and the first absorbance value as the absorbance value of the corresponding chemical reaction result.

[0010] Optionally, the free residual chlorine detection for each water sample to be detected in the detection work list also includes: when the absorbance value of the chemical reaction result exceeds the absorbance threshold of the free residual chlorine standard curve, diluting the water sample to be detected with a preset dilution factor; repeating the chemical reaction control until the absorbance value of the chemical reaction result determined after the diluted water sample to be detected and the corresponding detection reagent undergo a chemical reaction in the cuvette position meets the absorbance threshold of the free residual chlorine standard curve; determining the free residual chlorine concentration of the diluted water sample to be detected based on the absorbance value of the chemical reaction result and the free residual chlorine standard curve; and determining the free residual chlorine concentration of the water sample to be detected based on the free residual chlorine concentration of the diluted water sample to be detected and the preset dilution factor.

[0011] An embodiment of the present invention also provides a control device for detecting free residual chlorine in water, the control device comprising: a memory, a processor, and a computer program stored in the memory and executable on the processor, the processor executing the computer program to implement the above-mentioned method for detecting free residual chlorine in water.

[0012] An embodiment of the present invention further provides a machine-readable storage medium, characterized in that the machine-readable storage medium stores instructions, which enable the machine to execute the above-mentioned method for detecting free residual chlorine in water.

[0013] An embodiment of the present invention also provides a system for detecting free residual chlorine in water, the system for detecting free residual chlorine in water comprises the above-mentioned control device and an intermittent chemical analyzer, the intermittent chemical analyzer comprises a sample position, a reagent position, a cuvette position, a robotic arm and a cuvette cleaning tower.

[0014] Optionally, the system for detecting free residual chlorine in water also includes a human-computer interaction module, which is used to: input and / or modify relevant information of the water sample to be detected; construct and / or edit a detection work list including relevant information of multiple water samples to be detected; set the water sample to be detected to be diluted with a preset dilution multiple; and control the start and / or pause of free residual chlorine detection for each water sample to be detected in the detection work list.

[0015] Optionally, the system for detecting free residual chlorine in water also includes a display module, which is used to: display relevant information of the water sample to be tested; display a detection work list including relevant information of multiple water samples to be tested; display a free residual chlorine standard curve; and display a result list of free residual chlorine detection for each water sample to be tested in the detection work list.

[0016] Through the above technical scheme, the embodiment of the present invention is based on the automatic detection of free residual chlorine in water by an intermittent chemical analyzer. According to the construction of a detection work list including relevant information of multiple water samples to be detected, automatic free residual chlorine detection is performed on each water sample to be detected in the detection work list, thereby realizing efficient, rapid and accurate detection of free residual chlorine in water samples.

[0017] Other features and advantages of the embodiments of the present invention will be described in detail in the subsequent detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The accompanying drawings are used to provide a further understanding of the embodiments of the present invention and constitute a part of the specification. Together with the following specific implementations, they are used to explain the embodiments of the present invention, but do not constitute a limitation on the embodiments of the present invention. In the accompanying drawings:

[0019] Figure 1 It is a schematic diagram of the free residual chlorine detection in existing laboratories;

[0020] Figure 2 It is a schematic flow chart of a method for detecting free residual chlorine in water provided by an embodiment of the present invention;

[0021] Figure 3A and Figure 3B is a schematic diagram of an example detection work list;

[0022] Figure 4 is a schematic diagram of an example free residual chlorine standard curve;

[0023] Figure 5 It is a schematic diagram of the structure of a system for detecting free residual chlorine in water provided by an embodiment of the present invention;

[0024] Figure 6 is a schematic diagram of the structure of an example discontinuous chemical analyzer;

[0025] Figure 7 It is a schematic diagram of the detection interface parameters of the example system;

[0026] Figure 8 is a schematic diagram of the detection results of Example 1; and

[0027] Fig. 9 This is a schematic diagram of the detection results of Example 2.

[0028] Description of Reference Numerals

[0029] 10 Control device 20 Intermittent chemical analyzer DETAILED DESCRIPTION

[0030] The specific implementation of the embodiment of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described here is only used to illustrate and explain the embodiment of the present invention, and is not used to limit the embodiment of the present invention.

[0031] Before explaining the embodiments of the present invention in detail, the existing laboratory free residual chlorine detection technology is briefly introduced.

[0032] The most advanced laboratory free residual chlorine detection technology currently uses DPD powder pillow reagents and a chlorine rapid tester (a small single-parameter spectrophotometer) for manual detection, including: cleaning the sample bottle, replacing the sample bottle with the water sample to be tested 2 to 3 times, taking a certain amount (for example, 10 ml) of water sample into the sample bottle; putting it into the instrument and covering it with a light-shielding cover; first "reset" the instrument to zero to eliminate background interference such as turbidity and color in the water sample; using scissors to cut open a pack of solid DPD reagent powder pillows and carefully pour it into the sample bottle; shaking it well and coloring it for 1 minute, putting it into the colorimetric slot of the chlorine rapid tester, covering it with a light-shielding cover, and colorimetrically reading the reading; cleaning the sample bottle after the measurement is completed. The chlorine rapid tester is equipped with a DPD reagent pack.

[0033] Please refer to Figure 1 Taking a certain chlorine rapid tester as an example, the free chlorine detection method and operation process are as follows. Among them, the measurement range: 0.02-2.00mg / L Cl2; application range: used to test the residual chlorine (hypochlorous acid and hypochlorite ion) in water, treated water, river water and sea water.

[0034] 1. Select the test program and insert the adapter according to the detailed instructions of the instrument.

[0035] 2. Blank sample preparation: Add 10 mL of sample into the cuvette.

[0036] 3. Wipe the blank tube clean and put it into the sample pool. Zero: The instrument displays 0.00 mg / L (Cl2).

[0037] 4. Prepare the sample: Take another cuvette and add 10 mL of sample. Add a pack of DPD residual chlorine reagent powder pillow to the cuvette.

[0038] 5. Shake the cuvette repeatedly for 20 seconds to mix. If chlorine (Cl2) is present, the solution will appear pink.

[0039] 6. After adding the reagent, place the prepared sample tube into the sample pool within 1 minute, read the reading, and get the result.

[0040] The disadvantages of the above-mentioned DPD powder pillow reagent and residual chlorine rapid tester are as follows: 1) manual determination is inefficient; 2) the color development time of 1 minute is difficult to control in the specific experimental process, but the color development time has a significant impact on the results. Each time a powder pillow is cut open, the amount of solid powder poured out is inconsistent. In addition, if the solid powder cannot be completely dissolved, it may lead to inadequate reaction, etc., resulting in less than ideal precision and accuracy of the determination data; 3) the price of each package of solid DPD reagent is relatively high for laboratory analysis.

[0041] Figure 2 This is a flow chart of the method for detecting free residual chlorine in water provided by an embodiment of the present invention. Please refer to Figure 2 The method for detecting free residual chlorine in water may include the following steps:

[0042] Step S110: constructing a detection work list including relevant information of a plurality of water samples to be detected.

[0043] The method for detecting free residual chlorine in water is based on an intermittent chemical analyzer for detection, and the intermittent chemical analyzer may include a sample position, a reagent position, and a cuvette position. The relevant information of each water sample to be detected includes the following information: the water sample number, the sample position where the water sample is located, and the reagent position where the detection reagent corresponding to the water sample is located.

[0044] By way of example, a test work list can be generated based on multiple water samples to be tested for free residual chlorine content that need to be tested on the same day. Multiple test work lists for preset time periods can also be saved in advance. For example, if the water samples to be tested for free residual chlorine that need to be tested every day are fixed water samples, the test work list can be saved as, for example, an EXCEL table and called every day; if the water samples to be tested for free residual chlorine that need to be tested every day from Monday to Sunday are different, a test work list for Monday to Sunday can be established in advance, such as an EXCEL table, based on the multiple water samples to be tested for free residual chlorine content that need to be tested every day, so that the corresponding test work list can be called every day.

[0045] Preferably, the embodiment of the present invention also provides a process for automatically generating a detection work list. Figure 3AFor example, take the 23 water samples to be tested for free residual chlorine at 8:00 on a certain day, including domestic drinking water, 10 circulating water, membrane treated raw water, 10 reverse osmosis filtered water, recycled sewage, etc. as an example. The process of generating a test work list is as follows: For each water sample to be tested, enter the sample location of the water sample in the "Location" column; enter the water sample number and sample name or ID in the "Sample ID" column; select the "Residual Chlorine" analysis method in the method column (not shown in the figure); click "Save in Work List"; after editing the above 23 water samples to be tested, click "Next" to generate a test work list. Before 8:00 on a certain day, call the test work list, such as Figure 3B As shown, the free residual chlorine in the above 23 water samples to be tested can be automatically tested according to the test work list.

[0046] Preferably, before step S110, the method for detecting free residual chlorine in water may further include: diluting a residual chlorine standard solution of a preset concentration into a group of residual chlorine solutions by the intermittent chemical analyzer, wherein each residual chlorine solution in the group of residual chlorine solutions corresponds to a concentration; controlling the group of residual chlorine solutions to undergo a chemical reaction with a detection reagent of the same specification in the cuvette position, wherein the detection reagent of the same specification has the same concentration and the same dosage; for each residual chlorine solution in the group of residual chlorine solutions, after the chemical reaction is completed, reading the corresponding standard absorbance value; and drawing a free residual chlorine standard curve according to the standard absorbance value and the corresponding concentration of each residual chlorine solution.

[0047] According to the embodiment of the present invention, the concentration of free residual chlorine and the absorbance value read by the intermittent chemical analyzer are linearly related within a certain range, and the free residual chlorine is detected in the water sample to be detected. Therefore, it is necessary to determine the free residual chlorine standard curve according to the standard absorbance value and the corresponding concentration of the residual chlorine solution. Whether the free residual chlorine standard curve is good will directly affect the accuracy of the measurement result.

[0048] To illustrate with an example, a residual chlorine standard solution (e.g., residual chlorine standard liquid mother solution) of a preset concentration is placed in the No. 1 sample position of an intermittent chemical analyzer, and the residual chlorine standard liquid mother solution is quickly and accurately diluted into a group of residual chlorine solutions using the good automatic dilution function of the instrument. For example, taking the residual chlorine mother solution concentration as 1.2 mg / L as an example, the dilution multiple can be set to 20 times, 10 times, 8 times, 5 times, 3 times, 2 times, and 1 times, respectively, and the intermittent chemical analyzer automatically dilutes the solution to 0.06 mg / L, 0.12 mg / L, 0.15 mg / L, 0.24 mg / L, mg / L, 0.40 mg / L according to 0.60 mg / L, and 1.20 mg / L. Control the control group of residual chlorine solutions to react chemically with the detection reagent of the same specification in the cuvette position, and read the corresponding standard absorbance value according to the reaction color development, and draw the free residual chlorine standard curve through linear regression. The free residual chlorine standard curve can be expressed as: y=ax+b, where y represents the absorbance value, x represents the free residual chlorine concentration, and r represents the linear correlation coefficient of the standard curve. This value is generally required to be greater than 0.99, and the free residual chlorine standard curve meets the requirements.

[0049] Step S120: Control each water sample to be tested in the test work list and the corresponding detection reagent to perform a chemical reaction in the cuvette position, so as to perform free residual chlorine detection on each water sample to be tested in the test work list.

[0050] Continuing with the above example, before 8:00 on a certain day, the detection work list is called, such as Figure 3B As shown, check the interface to confirm that in the intermittent chemical analyzer, the sample positions, sample names, and reagent positions of the corresponding detection reagents R1 of the above 23 water samples to be tested are correct, then click "Batch Analysis Mode" to control the start of the intermittent chemical analyzer to automatically detect the free residual chlorine in the above 23 water samples to be tested, and obtain the determination results of the free residual chlorine. No manual intervention is required in the intermediate determination process.

[0051] Preferably, the free residual chlorine detection for each water sample to be detected in the detection work list may include: determining the absorbance value of the corresponding chemical reaction result for each water sample to be detected; and determining the concentration of free residual chlorine of the water sample to be detected based on the absorbance value of the chemical reaction result and the free residual chlorine standard curve.

[0052] Continuing with the above example, after clicking "Batch Analysis Mode", the intermittent chemical analyzer automatically starts, and controls its mechanical arm to automatically take samples and perform chemical reactions according to the order of the water samples to be tested in the test work list. Taking the first water sample to be tested as an example, extract, for example, 500 μL from the corresponding sample position and put it into a cuvette, and extract, for example, 100 μL from the corresponding reagent position where the detection reagent R1 is located and put it into a cuvette for chemical reaction. After a preset time, take the absorbance value of the corresponding chemical reaction result, and determine the free residual chlorine concentration x of the water sample to be tested based on the absorbance value y and the above-mentioned free residual chlorine standard curve, for example, y=ax+b.

[0053] Preferably, determining the absorbance value of the corresponding chemical reaction result may include: reading a first absorbance value of the water sample to be tested before conducting a chemical reaction; reading a second absorbance value of the corresponding post-reaction solution after the chemical reaction is completed; and determining the difference between the second absorbance value and the first absorbance value as the absorbance value of the corresponding chemical reaction result.

[0054] To illustrate with an example, the background deduction is automatically performed by an intermittent chemical analyzer to achieve the deduction of the background absorbance of the sample. Taking the first water sample to be tested as an example, 1) after extracting, for example, 500 μL from the corresponding sample position and placing it in a cuvette, read the first absorbance value of the water sample to be tested, for example, A0; 2) automatically add R1 reagent, and after the chemical reaction is complete, detect the absorbance value, for example, A1; 3) calculate the absorbance value A=A1-A0 generated by the free residual chlorine contained in the water sample to be tested; 4) according to the absorbance value y and the above-mentioned free residual chlorine standard curve, for example, y=ax+b, determine the concentration x of the free residual chlorine of the water sample to be tested.

[0055] Preferably, the free residual chlorine detection for each water sample to be detected in the detection work list may also include: when the absorbance value of the chemical reaction result exceeds the absorbance threshold of the free residual chlorine standard curve, diluting the water sample to be detected with a preset dilution factor; repeating the chemical reaction control until the absorbance value of the chemical reaction result determined after the diluted water sample to be detected and the corresponding detection reagent undergo a chemical reaction in the cuvette position meets the absorbance threshold of the free residual chlorine standard curve; determining the free residual chlorine concentration of the diluted water sample to be detected according to the absorbance value of the chemical reaction result and the free residual chlorine standard curve; and determining the free residual chlorine concentration of the water sample to be detected according to the free residual chlorine concentration of the diluted water sample to be detected and the preset dilution factor.

[0056] According to the above determination of the free residual chlorine standard curve, it can be known that the absorbance threshold of the free residual chlorine standard curve, that is, the threshold of x, can be determined according to the threshold of y (1.2 mg / L). When the concentration of free residual chlorine in the water sample to be detected exceeds 1.2 mg / L, that is, the absorbance value of the detected chemical reaction result exceeds the absorbance threshold of the free residual chlorine standard curve, the dilution function of the intermittent chemical analyzer can be used to dilute the water sample to be detected by an appropriate multiple before detection, for example, it can be automatically diluted by 50 ml of pure water arranged at position 48 of the reagent position. If the absorbance value of the chemical reaction result obtained by one dilution still exceeds the absorbance threshold of the free residual chlorine standard curve, multiple dilution tests can be performed to ensure that the absorbance value of the determined chemical reaction result meets the absorbance threshold of the free residual chlorine standard curve. The free residual chlorine concentration of the diluted water sample to be tested is determined according to the absorbance value of the chemical reaction result and the free residual chlorine standard curve; the free residual chlorine concentration of the water sample to be tested is determined according to the free residual chlorine concentration of the diluted water sample to be tested and the dilution multiple.

[0057] Furthermore, the embodiment of the present invention also provides the preparation of the detection reagent (or color developing reagent) R1. For example, 5 packages of hash free residual chlorine powder pillow are poured into a 20mL reagent bottle of the intermittent chemical analyzer, 5mL of distilled water is added, and the mixture is shaken to dissolve. 100μL of the detection reagent can be added to the reagent bottle of each reagent position. Considering that the sampling needle cannot completely remove all the reagents from the reagent bottle of the reagent position, the 5mL reagent can be used to react chemically with 40 water samples to be tested. The consumption of reagents will be greatly reduced, saving reagent costs.

[0058] Accordingly, the embodiment of the present invention is based on the automatic detection of free residual chlorine in water by the intermittent chemical analyzer. According to the construction of a detection work list including relevant information of a plurality of water samples to be detected, each water sample to be detected in the detection work list is automatically tested for free residual chlorine, so that efficient, rapid and accurate detection of free residual chlorine in water samples can be achieved. The problems of low analysis efficiency, less than ideal data precision and accuracy, high reagent cost, etc., which are currently used in laboratories of oil refining and chemical enterprises to determine residual chlorine, are solved. The embodiment of the present invention also provides a method for drawing a free residual chlorine standard curve according to the standard absorbance value and corresponding concentration of each residual chlorine solution, and determining the concentration of free residual chlorine of the water sample to be detected according to the absorbance value of the chemical reaction result and the free residual chlorine standard curve, so as to automatically obtain the test result.

[0059] An embodiment of the present invention also provides a control device for detecting free residual chlorine in water, the control device comprising: a memory, a processor, and a computer program stored in the memory and executable on the processor, the processor executing the computer program to implement the method for detecting free residual chlorine in water described in steps S110-S120.

[0060] An embodiment of the present invention further provides a machine-readable storage medium, on which instructions are stored, and the instructions enable a machine to execute the method for detecting free residual chlorine in water described in steps S110-S120.

[0061] Figure 5 This is a schematic diagram of the system structure for detecting free residual chlorine in water provided by an embodiment of the present invention. Please refer to Figure 5 The system for detecting free residual chlorine in water may include the above-mentioned control device 10 and intermittent chemical analyzer 20.

[0062] Please refer to Figure 6 The intermittent chemical analyzer may include a sample position, a reagent position, a cuvette position, a robotic arm and a cuvette cleaning tower.

[0063] Please refer to Figure 6 , to illustrate by way of example, the robotic arm of the intermittent chemical analyzer can automatically complete quantitative sampling from the designated sample position, taking reagents from the designated reagent position, adding reagents, etc. according to the control. The cuvette position includes, for example, 64 positions, and each water sample to be tested (including blank) completes a chemical reaction (color development reaction), reads the absorbance value (colorimetry), etc. in a different cuvette. If the batch of water samples to be tested is large, the intermittent chemical analyzer can clean the cuvette through a cuvette cleaning tower so that the cuvette can be recycled. The sample position includes, for example, 119 positions, and 119 water samples to be tested can be placed at one time. The reagent position includes, for example, 49 positions, and 50 ml of pure water can be arranged at position 48 of the reagent position for automatic dilution of the water sample to be tested, and 50 ml of pure water can be arranged at position 49 for reagent blank water, and the other 47 positions can be used to place reaction reagents.

[0064] Preferably, the system for detecting free residual chlorine in water also includes a human-computer interaction module, which is used to: input and / or modify relevant information of the water sample to be detected; construct and / or edit a detection work list including relevant information of multiple water samples to be detected; set the water sample to be detected to be diluted with a preset dilution multiple; and control the start and / or pause of free residual chlorine detection for each water sample to be detected in the detection work list.

[0065] By way of example, the human-computer interaction module can be used to input and / or modify relevant information of a water sample to be tested; can be used to construct and / or edit a test work list including relevant information of a plurality of water samples to be tested, such as Figure 3A As shown; it can also be used to set the dilution of the water sample to be tested at a preset dilution multiple, such as Figure 7 As shown; it can also be used to control the start and / or pause of free residual chlorine detection for each water sample to be detected in the detection work list.

[0066] Preferably, the system for detecting free residual chlorine in water also includes a display module, which is used to: display relevant information of the water sample to be detected; display a detection work list including relevant information of multiple water samples to be detected; display a free residual chlorine standard curve; and display a result list of free residual chlorine detection for each water sample to be detected in the detection work list.

[0067] By way of example, the display module can be used to display relevant information of the water sample to be tested, such as Figure 7 It can also be used to display a test work list including relevant information of multiple water samples to be tested, such as Figure 3B As shown; it can also be used to display the standard curve of free residual chlorine, such as Figure 4 It can also be used to display the result list of free residual chlorine detection for each water sample to be detected in the detection work list, such as Figure 8 and 9 shown.

[0068] Accordingly, the automatic detection system for free residual chlorine in water based on the discontinuous chemical analyzer in the embodiment of the present invention can automatically detect free residual chlorine for each water sample to be detected in the detection work list according to the construction of a detection work list including relevant information of a plurality of water samples to be detected, so as to realize efficient, rapid and accurate detection of free residual chlorine in water samples. The problems that the manual DPD spectrophotometry currently used in the laboratories of oil refining and chemical enterprises to determine the existence of residual chlorine are low in analysis efficiency, data precision and accuracy are not ideal, and reagent costs are high are solved. Based on the efficient, rapid and accurate detection of the discontinuous chemical analyzer, a faster and more accurate basis can be provided for the adjustment of chlorination agents in water treatment conditions.

[0069] The effects of the embodiments of the present invention are further illustrated by examples.

[0070] Example 1), 1) using the automatic detection system for free residual chlorine in water and the detection method for free residual chlorine in water according to the embodiments of the present invention, a certain water sample to be detected is detected six times in succession, that is, the constructed detection work list can include six identical water samples to be detected.

[0071] 2) Prepare a standard chlorine solution with a free residual chlorine content of about 1 mg / L to 1.5 mg / L using sodium hypochlorite, chlorine-free and other reagents to draw a free residual chlorine standard curve, and calibrate its accurate concentration using the iodine method. For example, the result of the iodine method calibration is 1.10 mg / L.

[0072] Pour the residual chlorine standard solution into the sample tube and place it in the No. 1 sample position of the intermittent chemical analyzer. Put a tube of distilled water in the No. 2 sample position. Use the dilution function to dilute the residual chlorine standard solution into a group of residual chlorine solutions, and automatically complete the drawing of the free residual chlorine standard curve.

[0073] According to the absorbance value y and the above-mentioned free residual chlorine standard curve, for example, y=ax+b, the free residual chlorine concentration x of the water sample to be tested is determined. The free residual chlorine standard curve is, for example: y=0.1715x+0.0164, wherein the linear correlation coefficient of the standard curve r=0.9996, and the free residual chlorine standard curve meets the requirements.

[0074] 3) Control each water sample to be tested in the detection work list and the corresponding detection reagent to perform a chemical reaction in the cuvette position to perform free residual chlorine detection on each water sample to be tested in the detection work list. For the above 6 water samples to be tested, determine the absorbance value of the corresponding chemical reaction result; according to the absorbance value of the chemical reaction result and the free residual chlorine standard curve, determine the concentration of free residual chlorine of the water sample to be tested, and the result is as follows: Figure 8 shown.

[0075] 4) At the same time, the existing Hash DPD powder pillow bag method was also used to manually perform parallel testing on the above 6 water samples to be tested. The test results are shown in Table 1.

[0076] Table 1 Analysis and comparison of the test results of the manual DPD spectrophotometry of the standard sample and the test results of the embodiment of the present invention

[0077]

[0078] By comparing the test results shown in Table 1, the precision of the data for the detection of free residual chlorine standard samples in the embodiment of the present invention is significantly better than that of the manual DPD powder pillow bag method. Precision is the prerequisite for accuracy. Therefore, the automatic detection system for free residual chlorine in water and the detection method for free residual chlorine in water in the embodiment of the present invention have good precision and high accuracy.

[0079] Example 2) The automatic detection system for free residual chlorine in water and the detection method for free residual chlorine in water according to the embodiments of the present invention are used to detect free residual chlorine in a variety of representative water samples that need to be sterilized by chlorination, such as domestic water leaving the factory, circulating water, filtered water, membrane-treated raw water, and membrane-treated intermediate water.

[0080] 1) Detect the free residual chlorine content in 8 representative water samples. The sample types include various types of water quality that need to be tested for free residual chlorine in oil refining and chemical enterprises, and 8 water samples to be tested, such as factory domestic water, circulating water, filtered water, membrane treatment raw water, membrane treatment intermediate water, etc. Construct a test work list including the relevant information of the above 8 water samples to be tested.

[0081] 2) The standard curve of free residual chlorine is shown in Example 1 and will not be described again here.

[0082] 3) Control each water sample to be tested in the detection work list and the corresponding detection reagent to perform a chemical reaction in the cuvette position to perform free residual chlorine detection on each water sample to be tested in the detection work list. For the above 6 water samples to be tested, determine the absorbance value of the corresponding chemical reaction result; according to the absorbance value of the chemical reaction result and the free residual chlorine standard curve, determine the concentration of free residual chlorine of the water sample to be tested, and the result is as follows: Fig. 9 shown.

[0083] At the same time, the existing Hash DPD powder pillow bag method was also used to manually perform parallel testing on the above 6 water samples to be tested. The test results are shown in Table 2.

[0084] Table 2 Analysis and comparison of the test results of manual DPD spectrophotometry and the embodiment of the present invention

[0085]

[0086]

[0087] By comparing the test results shown in Table 2, the data parallelism of the test of the free residual chlorine content in each actual sample using the embodiment of the present invention is better than that of the manual DPD powder pillow bag method, and the data deviation between the two is relatively small (<0.03 mg / L). The embodiment of the present invention is more suitable for the detection of free residual chlorine content in multiple water qualities such as circulating water, filtered water, membrane-treated raw water, and membrane-treated intermediate water that need to be sterilized by chlorination in petrochemical enterprises.

[0088] In summary, the automatic detection system for free residual chlorine in water and the detection method for free residual chlorine in water according to the embodiments of the present invention can solve the problems of low analysis efficiency, less than ideal data precision and accuracy, high reagent cost, etc., which are currently used in laboratories of oil refining and chemical enterprises to determine residual chlorine. And based on the efficient, fast and accurate determination of the fully automatic intermittent chemical analyzer, a faster and more accurate basis can be provided for the adjustment of chlorine dosing agents in water treatment conditions. The automatic detection system for free residual chlorine in water according to the embodiments of the present invention based on the fully automatic intermittent chemical analyzer can establish a more optimized automatic detection system for free residual chlorine in water after continuous experiments and explorations and parameter optimization.

[0089] Those skilled in the art will appreciate that the embodiments of the present application may be provided as methods, systems, or computer program products. Therefore, the present application may adopt the form of a complete hardware embodiment, a complete software embodiment, or an embodiment in combination with software and hardware. Moreover, the present application may adopt the form of a computer program product implemented in one or more computer-usable storage media (including but not limited to disk storage, CD-ROM, optical storage, etc.) that include computer-usable program code.

[0090] The present application is described with reference to the flowcharts and / or block diagrams of the methods, devices (systems), and computer program products according to the embodiments of the present application. It should be understood that each process and / or box in the flowchart and / or block diagram, as well as the combination of the processes and / or boxes in the flowchart and / or block diagram, can be implemented by computer program instructions. These computer program instructions can be provided to a processor of a general-purpose computer, a special-purpose computer, an embedded processor, or other programmable data processing device to generate a machine, so that the instructions executed by the processor of the computer or other programmable data processing device generate instructions for implementing the processes in the flowchart and / or block diagram. Figure 1 A process or multiple processes and / or boxes Figure 1 A device that provides the functions specified in a block or multiple blocks.

[0091] These computer program instructions may also be stored in a computer-readable memory capable of directing a computer or other programmable data processing device to operate in a specific manner, so that the instructions stored in the computer-readable memory produce an article of manufacture comprising an instruction device, which implements the process Figure 1 A process or multiple processes and / or boxes Figure 1 A function specified in one or more boxes.

[0092] These computer program instructions can also be loaded onto a computer or other programmable data processing device so that a series of operating steps are executed on the computer or other programmable device to produce a computer-implemented process, thereby providing instructions for implementing the process. Figure 1 A process or multiple processes and / or boxes Figure 1 The steps for the functions specified in one or more boxes.

[0093] In a typical configuration, a computing device includes one or more processors (CPU), input / output interfaces, network interfaces, and memory.

[0094] The memory may include non-permanent memory in a computer-readable medium, random access memory (RAM) and / or non-volatile memory in the form of read-only memory (ROM) or flash RAM. The memory is an example of a computer-readable medium.

[0095] Computer readable media include permanent and non-permanent, removable and non-removable media that can be implemented by any method or technology to store information. Information can be computer readable instructions, data structures, program modules or other data. Examples of computer storage media include, but are not limited to, phase change memory (PRAM), static random access memory (SRAM), dynamic random access memory (DRAM), other types of random access memory (RAM), read-only memory (ROM), electrically erasable programmable read-only memory (EEPROM), flash memory or other memory technology, compact disk read-only memory (CD-ROM), digital versatile disk (DVD) or other optical storage, magnetic cassettes, magnetic tape magnetic disk storage or other magnetic storage devices or any other non-transmission media that can be used to store information that can be accessed by a computing device. As defined herein, computer readable media does not include temporary computer readable media (transitory media), such as modulated data signals and carrier waves.

[0096] It should also be noted that the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, commodity or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, commodity or device. In the absence of more restrictions, the elements defined by the sentence "comprises a ..." do not exclude the existence of other identical elements in the process, method, commodity or device including the elements.

[0097] The above are only embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included within the scope of the claims of the present application.

Claims

1. A method for detecting free residual chlorine in water, characterized in that: The detection is performed based on an intermittent chemical analyzer, which includes a sample position, a reagent position, and a cuvette position. The method for detecting free residual chlorine in water includes: Constructing a detection work list including relevant information of a plurality of water samples to be detected, wherein the relevant information of each water sample to be detected includes information about: a water sample number, a sample position where the water sample is located, and a reagent position where a detection reagent corresponding to the water sample is located; and Each water sample to be detected in the detection work list and the corresponding detection reagent are controlled to perform a chemical reaction in the cuvette position, so as to perform free residual chlorine detection on each water sample to be detected in the detection work list.

2. The method for detecting free residual chlorine in water according to claim 1, characterized in that: Before constructing the detection work list including relevant information of a plurality of water samples to be detected, the method for detecting free residual chlorine in water further includes: Using the intermittent chemical analyzer, diluting a residual chlorine standard solution of a preset concentration into a group of residual chlorine solutions, each residual chlorine solution in the group of residual chlorine solutions corresponding to a concentration; Controlling the group of residual chlorine solutions to chemically react with a detection reagent of the same specification in the cuvette, wherein the detection reagent of the same specification has the same concentration and the same dosage; For each residual chlorine solution in the group of residual chlorine solutions, after the chemical reaction is completed, reading the corresponding standard absorbance value; and A free residual chlorine standard curve is drawn according to the standard absorbance value and corresponding concentration of each residual chlorine solution.

3. The method for detecting free residual chlorine in water according to claim 2, characterized in that: The free residual chlorine detection for each water sample to be detected in the detection work list comprises: For each water sample to be tested, determining the absorbance value of the corresponding chemical reaction result; and The concentration of free residual chlorine in the water sample to be tested is determined according to the absorbance value of the chemical reaction result and the free residual chlorine standard curve.

4. The method for detecting free residual chlorine in water according to claim 3, characterized in that: The absorbance value of the chemical reaction result is determined as follows: Before performing a chemical reaction, reading a first absorbance value of the water sample to be detected; After the chemical reaction is completed, reading a second absorbance value of the corresponding post-reaction solution; and The difference between the second absorbance value and the first absorbance value is determined as the absorbance value of the corresponding chemical reaction result.

5. The method for detecting free residual chlorine in water according to claim 3, characterized in that: The free residual chlorine detection for each water sample to be detected in the detection work list also includes: When the absorbance value of the chemical reaction result exceeds the absorbance threshold of the free residual chlorine standard curve, diluting the water sample to be tested by a preset dilution multiple; Repeat the chemical reaction control until the diluted water sample to be tested and the corresponding detection reagent react chemically in the cuvette, and the absorbance value of the determined chemical reaction result meets the absorbance threshold value of the free residual chlorine standard curve; Determining the concentration of free residual chlorine in the diluted water sample to be tested according to the absorbance value of the chemical reaction result and the free residual chlorine standard curve; and The concentration of free residual chlorine in the water sample to be tested is determined according to the concentration of free residual chlorine in the diluted water sample to be tested and the preset dilution factor.

6. A control device for detecting free residual chlorine in water, characterized in that: The control device includes: a memory, a processor, and a computer program stored in the memory and executable on the processor, and the processor executes the computer program to implement the method for detecting free residual chlorine in water according to any one of claims 1-5.

7. A machine-readable storage medium, characterized in that: The machine-readable storage medium stores instructions, which enable the machine to execute the method for detecting free residual chlorine in water according to any one of claims 1-5.

8. A system for detecting free residual chlorine in water, characterized in that: The system for detecting free residual chlorine in water comprises the control device and the intermittent chemical analyzer according to claim 6, The intermittent chemical analyzer comprises a sample position, a reagent position, a cuvette position, a mechanical arm and a cuvette cleaning tower.

9. The system for detecting free residual chlorine in water according to claim 8, characterized in that: The system for detecting free residual chlorine in water also includes a human-computer interaction module, which is used to: Enter and / or modify relevant information of the water samples to be tested; Constructing and / or editing a testing work list including relevant information of a plurality of water samples to be tested; Set to dilute the water sample to be tested at a preset dilution multiple; as well as Control the start and / or pause of free residual chlorine detection for each water sample to be detected in the detection work list.

10. The system for detecting free residual chlorine in water according to claim 8, characterized in that: The system for detecting free residual chlorine in water also includes a display module, which is used to: Display relevant information of the water sample to be tested; Displaying a testing work list including relevant information of a plurality of water samples to be tested; Display the standard curve of free residual chlorine; as well as Display a list of results of free residual chlorine testing for each water sample to be tested in the test work list.

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