Method and system for determining content of calcium and magnesium in zinc solution by chlor-amine method

Abstract

The application discloses a method and system for determining the content of calcium and magnesium in a zinc solution electrolyzed by a chlorine-ammonia method, and the method comprises the following steps: in a solution with PH equal to 10, taking sodium potassium tartrate and triethanolamine as masking agents, taking acid chrome blue K-naphthol green B as an indicator, titrating with EDTA until the solution is pure blue, and determining the total content of calcium and magnesium; in a strong alkaline solution with PH equal to or greater than 12, taking triethanolamine as a masking agent, taking a calcium indicator as an indicator, titrating with EDTA until the solution is pure blue, and determining the content of calcium. The method can accurately determine the content of calcium and magnesium in the zinc solution electrolyzed by the chlorine-ammonia method, is used for guiding the formula of a production raw material, and can timely remove calcium and magnesium in the solution, so that the production is not seriously affected.

Description

Technical Field

[0001] The present invention relates to the field of detection technology, and more specifically, to a method and system for determining the calcium and magnesium contents in a chloramine electrolytic zinc solution. Background Art

[0002] In the past, electrolytic zinc was produced using the acid method, and the determination of calcium and magnesium in the electrolytic zinc solution was mostly done by atomic absorption. However, the linearity of atomic absorption determination of calcium and magnesium in the chloramine electrolytic zinc solution was not very good, so the measured values ​​were significantly different from the true values. In addition, the use of atomic absorption to determine calcium and magnesium requires the advance purchase of corresponding equipment, such as an atomic absorption spectrometer, which is relatively expensive.

[0003] Therefore, the existing technology has defects and needs to be improved urgently. Summary of the Invention

[0004] In view of the above problems, the purpose of the present invention is to provide a method and system for determining the calcium and magnesium contents in a chlorine-ammonia electrolytic zinc solution, which can improve the determination accuracy of calcium and magnesium in a chlorine-ammonia electrolytic zinc solution and improve production efficiency.

[0005] The first aspect of the present invention provides a method for determining the calcium and magnesium contents in a zinc electrolytic solution using a chloramine process, comprising:

[0006] Obtaining a sample of zinc solution;

[0007] delivering the zinc solution sample to a plurality of conical flasks according to a preset first volume, to obtain a plurality of conical flasks containing the zinc solution;

[0008] Divide a plurality of conical flasks containing zinc solution into three groups, namely the first group, the second group and the third group;

[0009] The preset first combination of excipients is sequentially added to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1;

[0010] The preset second combination of excipients is sequentially added to the conical flask containing the zinc solution in the second group to obtain the EDTA consumption volume V2;

[0011] The preset third combination of excipients is sequentially added to the conical flask containing the zinc solution in the third group to obtain the EDTA consumption volume V3;

[0012] According to the EDTA consumption volumes V1, V2 and V3, the measured mass concentrations of calcium and magnesium in the corresponding zinc solution samples were obtained.

[0013] In this solution, the step of sequentially adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1 specifically includes:

[0014] Take any one Erlenmeyer flask containing zinc solution from the first group and set it as the first test Erlenmeyer flask;

[0015] Adding water, potassium sodium tartrate solution, triethanolamine solution, buffer solution and acid chrome blue K-naphthol green B indicator in the preset first combination of auxiliary materials to the first test conical flask in sequence to obtain a first mixed solution;

[0016] Titrate the EDTA standard solution in the preset first combination excipient into the first mixed solution, and acquire an image of the first mixed solution in real time;

[0017] extracting color feature values ​​from the image of the first mixed solution;

[0018] When the difference between the color feature value in the image of the first mixed solution and the preset first color feature value is less than the preset first color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(1-n) corresponding to the first test conical flask;

[0019] Traverse all the Erlenmeyer flasks containing zinc solution in the first group to obtain the first set of EDTA consumption volumes {V(1-1), V(1-2), ..., V(1-n)}, where 1-n represents the serial number of the Erlenmeyer flasks in the first group;

[0020] The formula for the EDTA consumption volume V1 is:

[0021] This plan also includes:

[0022] Calculate the difference between each value in the first set of EDTA consumption volumes and the EDTA consumption volume V1 to obtain a first volume difference value set;

[0023] Calculate the average value of the values ​​in the first volume difference value set to obtain a first volume average difference value;

[0024] Divide the first volume average difference by the EDTA consumption volume V1 to obtain the first volume average difference ratio;

[0025] If the first volume average difference ratio is less than or equal to a preset first volume average difference ratio threshold, the corresponding first set of EDTA consumption volumes is normal;

[0026] If the first volume average difference ratio is greater than a preset first volume average difference ratio threshold, then obtaining a sample volume multiple based on the preset first range within which the first volume average difference falls;

[0027] Multiplying the sample volume multiple by the preset first volume to obtain the zinc solution sample volume of the second first group, which is set as the second volume;

[0028] Inputting the second volume of the zinc solution sample into a preset conical flask to obtain a conical flask containing the second volume of the zinc solution, and constructing a second first group;

[0029] The preset first combination of excipients in multiples of the sample volume are sequentially added to the conical flask containing the second volume of zinc solution in the second first group to obtain the second first set of EDTA consumption volume {V ′ (1-1), V ′ (1-2),…,V ′ (1―n ′ )}, where 1-n ′ Indicates the number of the conical flask in the first group;

[0030] According to the first set of EDTA consumption volumes, the revised EDTA consumption volume V1 is obtained, which is set as V ′ 1, the formula is:

[0031]

[0032] Where k1 represents the sample volume multiple.

[0033] In this solution, the step of extracting the color feature value from the image of the first mixed solution specifically includes:

[0034] Extracting a set of pixel values ​​of pixel points in the image of the first mixed solution;

[0035] Calculating the difference between any two pixel values ​​in the pixel value set of the pixel points in the image of the first mixed solution to obtain a first pixel difference value set;

[0036] Comparing and analyzing the first pixel difference values ​​in the first pixel difference value set with the preset first pixel difference threshold value one by one, and marking the corresponding first pixel difference value if the first pixel difference value is greater than the preset first pixel difference threshold value;

[0037] Get the value of the first pixel difference of the marker;

[0038] When the number of the marked first pixel difference values ​​is greater than or equal to a preset first number threshold, pausing the titration of the EDTA standard solution, and reacquiring an image of the first mixed solution after a preset first time period;

[0039] When the number of the marked first pixel difference values ​​is less than a preset first number threshold, average pixel values ​​in a pixel value set of pixel points in the image of the first mixed solution are calculated to obtain an image pixel average value of the first mixed solution;

[0040] The average value of the pixels in the image of the first mixed solution is set as the color feature value in the image corresponding to the first mixed solution.

[0041] In this solution, the step of sequentially adding the preset second combination of excipients to the conical flask containing the zinc solution in the second group to obtain the EDTA consumption volume V2 specifically includes:

[0042] Take any one Erlenmeyer flask containing zinc solution from the second group and set it as the second test Erlenmeyer flask;

[0043] Sequentially add hydrochloric acid, ammonium fluoride, saturated thiourea solution, ascorbic acid, and acetic acid-sodium acetate buffer solution in the preset second combination of excipients to the second test conical flask to obtain a second mixed solution;

[0044] titrating the EDTA standard solution in the preset second combination excipient into the second mixed solution, and acquiring an image of the second mixed solution in real time;

[0045] extracting color feature values ​​from the image of the second mixed solution;

[0046] When the difference between the color feature value in the image of the second mixed solution and the preset second color feature value is less than the preset second color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(2-m) corresponding to the second test conical flask;

[0047] Traverse all the Erlenmeyer flasks containing zinc solution in the second group to obtain the second set of EDTA consumption volumes {V(2-1), V(2-2), ..., V(2-m)}, where 2-m represents the number of the Erlenmeyer flasks in the second group;

[0048] The formula for the EDTA consumption volume V2 is:

[0049] In this solution, the step of sequentially adding the preset third combination of excipients to the conical flask containing the zinc solution in the third group to obtain the EDTA consumption volume V3 specifically includes:

[0050] Take any one Erlenmeyer flask containing zinc solution from the third group and set it as the third test Erlenmeyer flask;

[0051] Sequentially add the triethanolamine solution, potassium hydroxide, and calcium indicator in the preset third combination of excipients to the third test conical flask to obtain a third mixed solution;

[0052] titrating the EDTA standard solution in the preset third combination excipient into the third mixed solution, and acquiring an image of the third mixed solution in real time;

[0053] extracting color feature values ​​from the image of the third mixed solution;

[0054] When the difference between the color feature value in the image of the third mixed solution and the preset third color feature value is less than the preset third color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(3-x) corresponding to the third test conical flask;

[0055] Traverse all the Erlenmeyer flasks containing zinc solution in the third group to obtain the third set of EDTA consumption volumes {V(3-1), V(3-2), ..., V(3-x)}, where 3-x represents the number of the Erlenmeyer flask in the third group;

[0056] The formula for the EDTA consumption volume V3 is:

[0057] In this scheme, the step of obtaining the measured mass concentrations of calcium and magnesium in the corresponding zinc solution sample based on the EDTA consumption volumes V1, V2 and V3 specifically includes:

[0058] The measured mass concentration of calcium is set to Ca (g / l), and the formula is:

[0059]

[0060] The measured mass concentration of magnesium is set to Mg (g / l), and the formula is:

[0061]

[0062] Where T (EDTA / Ca) Indicates the titer of EDTA to Ca in g / l, T (EDTA / Mg) Indicates the titer of EDTA to Mg in g / l, and V0 represents the preset first volume.

[0063] A second aspect of the present invention provides a system for determining the calcium and magnesium content in a zinc solution electrolyzed by ammonia chlorine method, comprising a memory and a processor. The memory stores a program for determining the calcium and magnesium content in a zinc solution electrolyzed by ammonia chlorine method. When the program is executed by the processor, the following steps are implemented:

[0064] Obtaining a sample of zinc solution;

[0065] delivering the zinc solution sample to a plurality of conical flasks according to a preset first volume, to obtain a plurality of conical flasks containing the zinc solution;

[0066] Divide a plurality of conical flasks containing zinc solution into three groups, namely the first group, the second group and the third group;

[0067] The preset first combination of excipients is sequentially added to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1;

[0068] The preset second combination of excipients is sequentially added to the conical flask containing the zinc solution in the second group to obtain the EDTA consumption volume V2;

[0069] The preset third combination of excipients is sequentially added to the conical flask containing the zinc solution in the third group to obtain the EDTA consumption volume V3;

[0070] According to the EDTA consumption volumes V1, V2 and V3, the measured mass concentrations of calcium and magnesium in the corresponding zinc solution samples were obtained.

[0071] In this solution, the step of sequentially adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1 specifically includes:

[0072] Take any one Erlenmeyer flask containing zinc solution from the first group and set it as the first test Erlenmeyer flask;

[0073] Adding water, potassium sodium tartrate solution, triethanolamine solution, buffer solution and acid chrome blue K-naphthol green B indicator in the preset first combination of auxiliary materials to the first test conical flask in sequence to obtain a first mixed solution;

[0074] Titrate the EDTA standard solution in the preset first combination excipient into the first mixed solution, and acquire an image of the first mixed solution in real time;

[0075] extracting color feature values ​​from the image of the first mixed solution;

[0076] When the difference between the color feature value in the image of the first mixed solution and the preset first color feature value is less than the preset first color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(1-n) corresponding to the first test conical flask;

[0077] Traverse all the Erlenmeyer flasks containing zinc solution in the first group to obtain the first set of EDTA consumption volumes {V(1-1), V(1-2), ..., V(1-n)}, where 1-n represents the serial number of the Erlenmeyer flasks in the first group;

[0078] The formula for the EDTA consumption volume V1 is:

[0079] This plan also includes:

[0080] Calculate the difference between each value in the first set of EDTA consumption volumes and the EDTA consumption volume V1 to obtain a first volume difference value set;

[0081] Calculate the average value of the values ​​in the first volume difference value set to obtain a first volume average difference value;

[0082] Divide the first volume average difference by the EDTA consumption volume V1 to obtain the first volume average difference ratio;

[0083] If the first volume average difference ratio is less than or equal to a preset first volume average difference ratio threshold, the corresponding first set of EDTA consumption volumes is normal;

[0084] If the first volume average difference ratio is greater than a preset first volume average difference ratio threshold, then obtaining a sample volume multiple based on the preset first range within which the first volume average difference falls;

[0085] Multiplying the sample volume multiple by the preset first volume to obtain the zinc solution sample volume of the second first group, which is set as the second volume;

[0086] Inputting the second volume of the zinc solution sample into a preset conical flask to obtain a conical flask containing the second volume of the zinc solution, and constructing a second first group;

[0087] The preset first combination of excipients in multiples of the sample volume are sequentially added to the conical flask containing the second volume of zinc solution in the second first group to obtain the second first set of EDTA consumption volume {V ′ (1-1), V ′ (1-2),…,V ′ (1―n ′ )}, where 1-n ′ Indicates the number of the conical flask in the first group;

[0088] According to the first set of EDTA consumption volumes, the revised EDTA consumption volume V1 is obtained, which is set as V ′ 1, the formula is:

[0089]

[0090] Where k1 represents the sample volume multiple.

[0091] The present invention discloses a method and system for determining the contents of calcium and magnesium in a chloramine electrolytic zinc solution. The method and system can accurately determine the contents of calcium and magnesium in the chloramine electrolytic zinc solution, thereby guiding the formulation of production raw materials and promptly removing calcium and magnesium from the liquid to avoid serious impact on production. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] Figure 1 A flow chart showing a method for determining the calcium and magnesium contents in a zinc electrolytic solution using a chloramine process according to the present invention is provided;

[0093] Figure 2 A flowchart showing the steps of extracting color feature values ​​from an image of a first mixed solution according to the present invention is shown;

[0094] Figure 3The block diagram of the system for measuring the calcium and magnesium contents in zinc electrolysis solution using the chloramine method of the present invention is shown. DETAILED DESCRIPTION

[0095] In order to more clearly understand the above-mentioned objects, features and advantages of the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be noted that, in the absence of conflict, the embodiments of the present application and the features therein can be combined with each other.

[0096] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the present invention is not limited to the specific embodiments disclosed below.

[0097] Figure 1 The present invention shows a flow chart of a method for determining the calcium and magnesium contents in a zinc electrolysis solution using the chloramine method.

[0098] like Figure 1 As shown, the present invention discloses a method for determining the calcium and magnesium contents in a zinc electrolytic solution using a chloramine method, comprising:

[0099] S101, obtaining a zinc solution sample;

[0100] S102, delivering the zinc solution sample to a plurality of conical flasks according to a preset first volume, to obtain a plurality of conical flasks containing the zinc solution;

[0101] S103, dividing the multiple conical flasks containing zinc solution into three groups, namely, a first group, a second group, and a third group;

[0102] S104, sequentially adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain an EDTA consumption volume V1;

[0103] S105, sequentially adding the preset second combination of excipients to the conical flask containing the zinc solution in the second group to obtain an EDTA consumption volume V2;

[0104] S106, sequentially adding the preset third combination of excipients to the conical flask containing the zinc solution in the third group to obtain an EDTA consumption volume V3;

[0105] S107, based on the EDTA consumption volumes V1, V2, and V3, obtain the measured mass concentrations of calcium and magnesium in the corresponding zinc solution sample.

[0106] According to an embodiment of the present invention, the number of the conical flasks is no less than 6, and the number of conical flasks containing zinc solution in each group is no less than 2. The conical flasks are transparent, and the color of the liquid in the conical flasks can be directly observed.

[0107] According to an embodiment of the present invention, the step of sequentially adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1 specifically includes:

[0108] Take any one Erlenmeyer flask containing zinc solution from the first group and set it as the first test Erlenmeyer flask;

[0109] Adding water, potassium sodium tartrate solution, triethanolamine solution, buffer solution and acid chrome blue K-naphthol green B indicator in the preset first combination of auxiliary materials to the first test conical flask in sequence to obtain a first mixed solution;

[0110] Titrate the EDTA standard solution in the preset first combination excipient into the first mixed solution, and acquire an image of the first mixed solution in real time;

[0111] extracting color feature values ​​from the image of the first mixed solution;

[0112] When the difference between the color feature value in the image of the first mixed solution and the preset first color feature value is less than the preset first color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(1-n) corresponding to the first test conical flask;

[0113] Traverse all the Erlenmeyer flasks containing zinc solution in the first group to obtain the first set of EDTA consumption volumes {V(1-1), V(1-2), ..., V(1-n)}, where 1-n represents the serial number of the Erlenmeyer flasks in the first group;

[0114] The formula for the EDTA consumption volume V1 is:

[0115] It should be noted that, in this embodiment, the first volume is preset to be 2 ml, the water in the preset first combination of auxiliary materials is 50 ml, the potassium sodium tartrate solution is 1 ml, the triethanolamine solution is 5 ml, the buffer solution is 10 ml, and the acid chrome blue K-naphthol green B indicator is 0.1 g; the buffer solution (PH = 10) is 67.5 g ammonium chloride dissolved in 300 ml l A mixed solution obtained by adding 570 ml of concentrated ammonia to carbon dioxide-free distilled water and diluting the mixture to 1000 ml with water; the potassium sodium tartrate solution is a 10% aqueous solution; the triethanolamine solution is a 1+2 aqueous solution; the acid chrome blue K-naphthol green B indicator is a crushed mixture of 0.3 g of acid chrome blue K, 0.75 g of naphthol green B, and 50 g of potassium nitrate dried at 105°C; a preset first volume of zinc solution sample and a preset first combination of auxiliary materials, water, potassium sodium tartrate solution, triethanolamine solution, buffer solution, and acid chrome blue K-naphthol green B indicator are mixed in sequence to obtain a first mixed solution; the preset first color characteristic value is the pixel value corresponding to pure blue.

[0116] According to an embodiment of the present invention, the further embodiment includes:

[0117] Calculate the difference between each value in the first set of EDTA consumption volumes and the EDTA consumption volume V1 to obtain a first volume difference value set;

[0118] Calculate the average value of the values ​​in the first volume difference value set to obtain a first volume average difference value;

[0119] Divide the first volume average difference by the EDTA consumption volume V1 to obtain the first volume average difference ratio;

[0120] If the first volume average difference ratio is less than or equal to a preset first volume average difference ratio threshold, the corresponding first set of EDTA consumption volumes is normal;

[0121] If the first volume average difference ratio is greater than a preset first volume average difference ratio threshold, then obtaining a sample volume multiple based on the preset first range within which the first volume average difference falls;

[0122] Multiplying the sample volume multiple by the preset first volume to obtain the zinc solution sample volume of the second first group, which is set as the second volume;

[0123] Inputting the second volume of the zinc solution sample into a preset conical flask to obtain a conical flask containing the second volume of the zinc solution, and constructing a second first group;

[0124] The preset first combination of excipients in multiples of the sample volume are sequentially added to the conical flask containing the second volume of zinc solution in the second first group to obtain the second first set of EDTA consumption volume {V ′ (1-1), V ′ (1-2),…,V ′ (1―n ′ )}, where 1-n ′ Indicates the number of the conical flask in the first group;

[0125] According to the first set of EDTA consumption volumes, the revised EDTA consumption volume V1 is obtained, which is set as V ′ 1, the formula is:

[0126]

[0127] Where k1 represents the sample volume multiple.

[0128] It should be noted that the value in the first volume difference value set is the absolute value of the difference between the value in the first EDTA consumption volume set and the EDTA consumption volume V1. When the first EDTA consumption volume set is normal, the corresponding EDTA consumption volume V1 is normal. For example, if the preset first volume average difference ratio threshold is 0.03, if the preset first range division cardinality is 0.02, the preset first range can be divided into (0, 0.03], (0.03, 0.05], (0.05, 0.07], (0.07, 0.09] ]…and so on. For example, the preset first range (0, 0.03] corresponds to a sample volume multiple of 1, the preset first range (0.03, 0.05] corresponds to a sample volume multiple of 2, and so on. The larger the value in the preset first range, the larger the sample volume multiple of the corresponding preset first range. The sample volume multiple corresponding to (0, 0.03] is 1, that is, the first volume average difference ratio is less than or equal to the preset first volume average difference ratio threshold. When the sample volume multiple is 1, there is no need to adjust the EDTA consumption volume V1.

[0129] It should be noted that after the EDTA consumption volumes V2 and V3 are calculated, the comparison and analysis method of the above-mentioned first volume average difference ratio and the preset first volume average difference ratio threshold is used to determine whether the second or third set of EDTA consumption volumes are normal. If not, the same method is used for measurement and adjustment.

[0130] Figure 2 A flow chart showing the steps of extracting color feature values ​​from an image of a first mixed solution according to the present invention is shown.

[0131] like Figure 2 As shown, the step of extracting the color feature value from the image of the first mixed solution specifically includes:

[0132] S201, extracting a pixel value set of pixel points in an image of the first mixed solution;

[0133] S202, performing difference calculation on any two pixel values ​​in a pixel value set of pixel points in the image of the first mixed solution to obtain a first pixel difference value set;

[0134] S203, comparing and analyzing each first pixel difference in the first pixel difference set with a preset first pixel difference threshold, and marking the corresponding first pixel difference if the first pixel difference is greater than the preset first pixel difference threshold;

[0135] S204, obtaining the quantity value of the marked first pixel difference;

[0136] S205, when the number of the marked first pixel difference values ​​is greater than or equal to a preset first number threshold, pausing the titration of the EDTA standard solution, and reacquiring an image of the first mixed solution after a preset first time period;

[0137] S206, when the number of the marked first pixel differences is less than a preset first number threshold, calculating the mean of the pixel values ​​in the pixel value set of the pixel points in the image of the first mixed solution to obtain an average value of the image pixels of the first mixed solution;

[0138] S207: Setting the average value of the pixels in the image of the first mixed solution as the color feature value in the image corresponding to the first mixed solution.

[0139] It should be noted that when the number of the marked first pixel difference values ​​is greater than or equal to the preset first number threshold, it indicates that the chemical reaction in the first mixed solution is not yet complete. Therefore, it is necessary to re-acquire the image of the first mixed solution after a preset first time period for re-judgment.

[0140] Furthermore, after pausing the titration of the EDTA standard solution, the position of the pixel value corresponding to the first pixel difference of the mark is determined in the image of the first mixed solution according to the marked first pixel difference, and is set as the marked position; the image of the first mixed solution is divided according to a preset grid size to obtain multiple sub-images of the first mixed solution, and the quantity values ​​of the marked positions in the sub-images of the first mixed solution are extracted; the quantity values ​​of the marked positions in any two sub-images of the first mixed solution are calculated to obtain the quantity difference of the marked positions; if the quantity difference of the marked positions is less than or equal to a preset second quantity threshold, the test environment temperature value is obtained; if the test environment temperature value is within the preset temperature value range, it is allowed to re-acquire the image of the first mixed solution after a preset first time period; if the test environment temperature value is not within the preset temperature value range, the test environment temperature value is adjusted to the preset temperature value range based on the preset temperature regulation control device. Afterwards, the image of the first mixed solution is reacquired. If the temperature adjustment time is greater than or equal to the preset first time period, the image of the first mixed solution is reacquired after the test environment temperature value reaches the preset temperature value range. If the temperature adjustment time is less than the preset first time period, the image of the first mixed solution is reacquired after the preset first time period is subtracted from the temperature adjustment time. If the quantity difference of the mark positions is greater than the preset second quantity threshold, the shaking prompt information is triggered, and based on the shaking prompt information, the conical flask is shaken to promote the chemical reaction of the first mixed solution. After the shaking of the conical flask is completed and the first mixed solution is left to stand, the corresponding time is recorded and set as the second time. If the second time is greater than or equal to the preset first time period, the image of the first mixed solution is allowed to be reacquired. If the second time is less than the preset first time period, the image of the first mixed solution is reacquired after the preset first time period is subtracted from the second time.

[0141] Furthermore, if after a preset second number of preset first time periods, the number of marked first pixel differences in the reacquired image of the first mixed solution is still greater than or equal to a preset third number threshold, the test data of the conical flask with the corresponding number is deleted.

[0142] Furthermore, the quantity value of the test data of the deleted conical flask is extracted and set as the fourth quantity value; if the fourth quantity value is greater than or equal to the preset fourth quantity threshold, the preset first combination excipient detection information is triggered; based on the preset first combination excipient detection information, the reagent material in the preset first combination excipient is detected and identified.

[0143] Furthermore, when the fourth quantity value is less than a preset fourth quantity threshold, the quantity value of the test data of the remaining conical flasks is extracted and set as a fifth quantity value. If the fifth quantity value is less than the preset fifth quantity threshold, it is triggered to increase the quantity information of the first group or the second first group of conical flasks. Based on the increase of the quantity information of the first group or the second first group of conical flasks, the number of conical flasks containing zinc solution samples in the first group or the second first group is increased.

[0144] According to an embodiment of the present invention, the step of sequentially adding the preset second combination of excipients to the conical flask containing the zinc solution in the second group to obtain the EDTA consumption volume V2 specifically includes:

[0145] Take any one Erlenmeyer flask containing zinc solution from the second group and set it as the second test Erlenmeyer flask;

[0146] Sequentially add hydrochloric acid, ammonium fluoride, saturated thiourea solution, ascorbic acid, and acetic acid-sodium acetate buffer solution in the preset second combination of excipients to the second test conical flask to obtain a second mixed solution;

[0147] titrating the EDTA standard solution in the preset second combination excipient into the second mixed solution, and acquiring an image of the second mixed solution in real time;

[0148] extracting color feature values ​​from the image of the second mixed solution;

[0149] When the difference between the color feature value in the image of the second mixed solution and the preset second color feature value is less than the preset second color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(2-m) corresponding to the second test conical flask;

[0150] Traverse all the Erlenmeyer flasks containing zinc solution in the second group to obtain the second set of EDTA consumption volumes {V(2-1), V(2-2), ..., V(2-m)}, where 2-m represents the number of the Erlenmeyer flasks in the second group;

[0151] The formula for the EDTA consumption volume V2 is:

[0152] It should be noted that, in this embodiment, the preset first volume is 2 ml, the preset second combination of auxiliary materials includes 1 ml of hydrochloric acid, 0.2 g of ammonium fluoride, 10 ml of thiourea saturated solution, 0.2 g of ascorbic acid, and 25 ml of acetic acid-sodium acetate buffer solution; the hydrochloric acid is ρ = 1.19 g / l; the acetic acid-sodium acetate buffer solution (pH 5.5-6.0) is prepared by dissolving 2000 g of sodium acetate in water, adding 100 ml of glacial acetic acid, and then diluting with water to 10000 ml; a zinc solution sample of the preset first volume and a sample of hydrochloric acid, ammonium fluoride, saturated thiourea solution, ascorbic acid and acetic acid-sodium acetate buffer solution in the preset second combination of auxiliary materials are mixed in sequence to obtain a second mixed solution, and the preset second color feature value is the pixel value corresponding to bright yellow.

[0153] According to an embodiment of the present invention, the step of sequentially adding the preset third combination of excipients to the conical flask containing the zinc solution in the third group to obtain the EDTA consumption volume V3 specifically includes:

[0154] Take any one Erlenmeyer flask containing zinc solution from the third group and set it as the third test Erlenmeyer flask;

[0155] Sequentially add the triethanolamine solution, potassium hydroxide, and calcium indicator in the preset third combination of excipients to the third test conical flask to obtain a third mixed solution;

[0156] titrating the EDTA standard solution in the preset third combination excipient into the third mixed solution, and acquiring an image of the third mixed solution in real time;

[0157] extracting color feature values ​​from the image of the third mixed solution;

[0158] When the difference between the color feature value in the image of the third mixed solution and the preset third color feature value is less than the preset third color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(3-x) corresponding to the third test conical flask;

[0159] Traverse all the Erlenmeyer flasks containing zinc solution in the third group to obtain the third set of EDTA consumption volumes {V(3-1), V(3-2), ..., V(3-x)}, where 3-x represents the number of the Erlenmeyer flask in the third group;

[0160] The formula for the EDTA consumption volume V3 is:

[0161] It should be noted that the triethanolamine solution in the preset third combination of auxiliary materials is 5 ml, the calcium indicator is 0.1 g, the pH of the third mixed solution is adjusted to above 12 by potassium hydroxide, the triethanolamine solution is a 1+2 aqueous solution, and the potassium hydroxide is a 20% aqueous solution; a preset first volume of zinc solution sample and a preset third combination of auxiliary materials, triethanolamine solution, potassium hydroxide and calcium indicator are mixed in sequence to obtain a third mixed solution, and the preset third color characteristic value is the pixel value corresponding to pure blue.

[0162] According to an embodiment of the present invention, the step of obtaining the measured mass concentrations of calcium and magnesium in the corresponding zinc solution sample based on the EDTA consumption volumes V1, V2, and V3 specifically includes:

[0163] The measured mass concentration of calcium is set to Ca (g / l), and the formula is:

[0164]

[0165] The measured mass concentration of magnesium is set to Mg (g / l), and the formula is:

[0166]

[0167] Where T (EDTA / Ca) Indicates the titer of EDTA to Ca in g / l, T (EDTA / Mg) Indicates the titer of EDTA to Mg in g / l, and V0 represents the preset first volume.

[0168] It should be noted that if the EDTA consumption volume V1, V2 or V3 is revised, the revised EDTA consumption volume V1, V2 or V3 should be directly used to replace V1, V2 or V3 in the Ca (g / l) calculation formula. For example, the revised EDTA consumption volume V1 is set to V ′ 1, then the formula for calculating Mg (g / l) is revised to:

[0169] Figure 3 The block diagram of the system for measuring the calcium and magnesium contents in zinc electrolysis solution using the chloramine method of the present invention is shown.

[0170] like Figure 3 As shown, the second aspect of the present invention provides a system 3 for determining the content of calcium and magnesium in a zinc solution electrolyzed by ammonia chlorine method, comprising a memory 31 and a processor 32. The memory stores a program for determining the content of calcium and magnesium in a zinc solution electrolyzed by ammonia chlorine method. When the program is executed by the processor, the following steps are implemented:

[0171] Obtaining a sample of zinc solution;

[0172] delivering the zinc solution sample to a plurality of conical flasks according to a preset first volume, to obtain a plurality of conical flasks containing the zinc solution;

[0173] Divide a plurality of conical flasks containing zinc solution into three groups, namely the first group, the second group and the third group;

[0174] The preset first combination of excipients is sequentially added to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1;

[0175] The preset second combination of excipients is sequentially added to the conical flask containing the zinc solution in the second group to obtain the EDTA consumption volume V2;

[0176] The preset third combination of excipients is sequentially added to the conical flask containing the zinc solution in the third group to obtain the EDTA consumption volume V3;

[0177] According to the EDTA consumption volumes V1, V2 and V3, the measured mass concentrations of calcium and magnesium in the corresponding zinc solution samples were obtained.

[0178] In this solution, the step of sequentially adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1 specifically includes:

[0179] Take any one Erlenmeyer flask containing zinc solution from the first group and set it as the first test Erlenmeyer flask;

[0180] Adding water, potassium sodium tartrate solution, triethanolamine solution, buffer solution and acid chrome blue K-naphthol green B indicator in the preset first combination of auxiliary materials to the first test conical flask in sequence to obtain a first mixed solution;

[0181] Titrate the EDTA standard solution in the preset first combination excipient into the first mixed solution, and acquire an image of the first mixed solution in real time;

[0182] extracting color feature values ​​from the image of the first mixed solution;

[0183] When the difference between the color feature value in the image of the first mixed solution and the preset first color feature value is less than the preset first color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(1-n) corresponding to the first test conical flask;

[0184] Traverse all the Erlenmeyer flasks containing zinc solution in the first group to obtain the first set of EDTA consumption volumes {V(1-1), V(1-2), ..., V(1-n)}, where 1-n represents the serial number of the Erlenmeyer flasks in the first group;

[0185] The formula for the EDTA consumption volume V1 is:

[0186] This plan also includes:

[0187] Calculate the difference between each value in the first set of EDTA consumption volumes and the EDTA consumption volume V1 to obtain a first volume difference value set;

[0188] Calculate the average value of the values ​​in the first volume difference value set to obtain a first volume average difference value;

[0189] Divide the first volume average difference by the EDTA consumption volume V1 to obtain the first volume average difference ratio;

[0190] If the first volume average difference ratio is less than or equal to a preset first volume average difference ratio threshold, the corresponding first set of EDTA consumption volumes is normal;

[0191] If the first volume average difference ratio is greater than a preset first volume average difference ratio threshold, then obtaining a sample volume multiple based on the preset first range within which the first volume average difference falls;

[0192] Multiplying the sample volume multiple by the preset first volume to obtain the zinc solution sample volume of the second first group, which is set as the second volume;

[0193] Inputting the second volume of the zinc solution sample into a preset conical flask to obtain a conical flask containing the second volume of the zinc solution, and constructing a second first group;

[0194] The preset first combination of excipients in multiples of the sample volume are sequentially added to the conical flask containing the second volume of zinc solution in the second first group to obtain the second first set of EDTA consumption volume {V ′ (1-1), V ′ (1-2),…,V ′ (1―n ′ )}, where 1-n ′ Indicates the number of the conical flask in the first group;

[0195] According to the first set of EDTA consumption volumes, the revised EDTA consumption volume V1 is obtained, which is set as V ′ 1, the formula is:

[0196]

[0197] Where k1 represents the sample volume multiple.

[0198] The present invention discloses a method and system for determining the contents of calcium and magnesium in a chloramine electrolytic zinc solution. The method and system can accurately determine the contents of calcium and magnesium in the chloramine electrolytic zinc solution, thereby guiding the formulation of production raw materials and promptly removing calcium and magnesium from the liquid to avoid serious impact on production.

[0199] In the several embodiments provided in this application, it should be understood that the disclosed devices and methods can be implemented in other ways. The device embodiments described above are merely schematic. For example, the division of the units is merely a logical function division. In actual implementation, there may be other division methods, such as: multiple units or components can be combined, or can be integrated into another system, or some features can be ignored or not executed. In addition, the coupling, direct coupling, or communication connection between the components shown or discussed can be through some interfaces, and the indirect coupling or communication connection of the devices or units can be electrical, mechanical or other forms.

[0200] The units described above as separate components may or may not be physically separated, and the components displayed as units may or may not be physical units; they may be located in one place or distributed across multiple network units; some or all of the units may be selected according to actual needs to achieve the purpose of the scheme of this embodiment.

[0201] In addition, all functional units in the embodiments of the present invention may be integrated into one processing unit, or each unit may be separately used as a unit, or two or more units may be integrated into one unit; the above-mentioned integrated units may be implemented in the form of hardware or in the form of hardware plus software functional units.

[0202] Those skilled in the art will appreciate that all or part of the steps of the above-mentioned method embodiments may be implemented by hardware associated with program instructions, and the aforementioned program may be stored in a computer-readable storage medium. When the program is executed, the program executes the steps of the above-mentioned method embodiments. The aforementioned storage medium includes various media that can store program codes, such as mobile storage devices, read-only memories (ROMs), random access memories (RAMs), magnetic disks, or optical disks.

[0203] Alternatively, if the above-mentioned integrated unit of the present invention is implemented in the form of a software functional module and sold or used as an independent product, it can also be stored in a computer-readable storage medium. Based on this understanding, the technical solution of the embodiment of the present invention, or the part that contributes to the prior art, can be embodied in the form of a software product. The computer software product is stored in a storage medium and includes a number of instructions for enabling a computer device (which can be a personal computer, server, or network device, etc.) to execute all or part of the methods described in each embodiment of the present invention. The aforementioned storage medium includes: various media that can store program codes, such as mobile storage devices, ROM, RAM, magnetic disks or optical disks.

Claims

1. A method for determining the calcium and magnesium contents in a chloramine electrolytic zinc solution, comprising: Obtaining a sample of zinc solution; delivering the zinc solution sample to a plurality of conical flasks according to a preset first volume, to obtain a plurality of conical flasks containing zinc solution; Divide a plurality of conical flasks containing zinc solution into three groups, namely the first group, the second group and the third group; Add the preset first combination of excipients sequentially into the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1; The step of sequentially adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1 specifically includes: Take any one Erlenmeyer flask containing zinc solution from the first group and set it as the first test Erlenmeyer flask; Adding water, potassium sodium tartrate solution, triethanolamine solution, buffer solution and acid chrome blue K-naphthol green B indicator in the preset first combination of auxiliary materials to the first test conical flask in sequence to obtain a first mixed solution; Titrate the EDTA standard solution in the preset first combination of excipients into the first mixed solution to obtain the EDTA consumption volume V (1-n) corresponding to the first test conical flask; Traverse all the conical flasks containing zinc solution in the first group and obtain the first set of EDTA consumption volume , where 1-n represents the number of the conical flask in the first group; The formula for the EDTA consumption volume V1 is: ; The method further includes: performing difference calculation on each of the values ​​in the first set of EDTA consumption volumes and the EDTA consumption volume V1 to obtain a first volume difference value set; Calculate the average value of the values ​​in the first volume difference value set to obtain a first volume average difference value; Divide the first volume average difference by the EDTA consumption volume V1 to obtain the first volume average difference ratio; If the first volume average difference ratio is less than or equal to a preset first volume average difference ratio threshold, the corresponding first set of EDTA consumption volumes is normal; If the first volume average difference ratio is greater than a preset first volume average difference ratio threshold, then obtaining a sample volume multiple based on the preset first range within which the first volume average difference falls; Multiplying the sample volume multiple by the preset first volume to obtain the zinc solution sample volume of the second first group, which is set as the second volume; Inputting the second volume of the zinc solution sample into a preset conical flask to obtain a conical flask containing the second volume of the zinc solution, and constructing a second first group; The preset first combination of excipients in multiples of the sample volume are sequentially added to the conical flask containing the second volume of zinc solution in the second first group to obtain the second first set of EDTA consumption volume. ,in Indicates the number of the conical flask in the first group; According to the first set of EDTA consumption volumes, the revised EDTA consumption volume V1 is obtained, which is set as , the formula is: in Indicates the sample volume multiple; Sequentially adding a preset second combination of excipients to the conical flask containing the zinc solution in the second group to obtain an EDTA consumption volume V2; the preset second group of excipients includes hydrochloric acid, ammonium fluoride, saturated thiourea solution, ascorbic acid, acetic acid-sodium acetate buffer solution and EDTA standard solution; Sequentially adding a preset third combination of excipients to the conical flask containing the zinc solution in the third group to obtain an EDTA consumption volume V3; the preset third combination of excipients includes triethanolamine solution, potassium hydroxide, calcium indicator and EDTA standard solution; According to the EDTA consumption volumes V1, V2 and V3, the measured mass concentrations of calcium and magnesium in the corresponding zinc solution samples were obtained.

2. The method for determining the contents of calcium and magnesium in a chlorine-ammonia electrolytic zinc solution according to claim 1, further comprising: acquiring an image of the first mixed solution in real time; extracting color feature values ​​from the image of the first mixed solution; When the difference between the color characteristic value in the image of the first mixed solution and the preset first color characteristic value is less than the preset first color difference threshold, the titration of the corresponding EDTA standard solution is stopped.

3. The method for determining the calcium and magnesium contents in a zinc electrolytic solution using the chlorine-ammonia process according to claim 2, wherein the step of extracting color feature values ​​from the image of the first mixed solution comprises: Extracting a set of pixel values ​​of pixel points in the image of the first mixed solution; Calculating the difference between any two pixel values ​​in the pixel value set of the pixel points in the image of the first mixed solution to obtain a first pixel difference value set; Comparing and analyzing the first pixel difference values ​​in the first pixel difference value set with the preset first pixel difference threshold value one by one, and marking the corresponding first pixel difference value if the first pixel difference value is greater than the preset first pixel difference threshold value; Get the value of the first pixel difference of the marker; When the number of the marked first pixel difference values ​​is greater than or equal to a preset first number threshold, pausing the titration of the EDTA standard solution, and reacquiring an image of the first mixed solution after a preset first time period; When the number of the marked first pixel difference values ​​is less than a preset first number threshold, average pixel values ​​in a pixel value set of pixel points in the image of the first mixed solution are calculated to obtain an image pixel average value of the first mixed solution; The average value of the pixels in the image of the first mixed solution is set as the color feature value in the image corresponding to the first mixed solution.

4. The method for determining the calcium and magnesium contents in a zinc electrolytic solution using the chloramine process according to claim 1, wherein the step of sequentially adding the preset second combination of auxiliary materials to the conical flask containing the zinc solution in the second group to obtain the EDTA consumption volume V2 specifically comprises: Take any one Erlenmeyer flask containing zinc solution from the second group and set it as the second test Erlenmeyer flask; Sequentially add hydrochloric acid, ammonium fluoride, saturated thiourea solution, ascorbic acid, and acetic acid-sodium acetate buffer solution in the preset second combination of excipients to the second test conical flask to obtain a second mixed solution; titrating the EDTA standard solution in the preset second combination excipient into the second mixed solution, and acquiring an image of the second mixed solution in real time; extracting color feature values ​​from the image of the second mixed solution; When the difference between the color feature value in the image of the second mixed solution and the preset second color feature value is less than the preset second color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V (2-m) corresponding to the second test conical flask; Traverse all the conical flasks containing zinc solution in the second group to obtain the EDTA consumption volume of the second set , where 2-m represents the number of the conical flask in the second group; The formula for the EDTA consumption volume V2 is: .

5. The method for determining the calcium and magnesium contents in a zinc electrolytic solution by the chloramine process according to claim 1, wherein the step of sequentially adding the preset third combination of auxiliary materials to the conical flask containing the zinc solution in the third group to obtain the EDTA consumption volume V3 specifically comprises: Take any one Erlenmeyer flask containing zinc solution from the third group and set it as the third test Erlenmeyer flask; Sequentially add the triethanolamine solution, potassium hydroxide, and calcium indicator in the preset third combination of excipients to the third test conical flask to obtain a third mixed solution; titrating the EDTA standard solution in the preset third combination excipient into the third mixed solution, and acquiring an image of the third mixed solution in real time; extracting color feature values ​​from the image of the third mixed solution; When the difference between the color feature value in the image of the third mixed solution and the preset third color feature value is less than the preset third color difference threshold, the titration of the corresponding EDTA standard solution is stopped to obtain the EDTA consumption volume V(3-x) corresponding to the third test conical flask; Traverse all the conical flasks containing zinc solution in the third group to obtain the third set of EDTA consumption volume , where 3-x represents the number of the conical flask in the third group; The formula for the EDTA consumption volume V3 is: .

6. The method for determining the calcium and magnesium contents in a zinc solution electrolyzed by the chloramine process according to claim 1, wherein the step of obtaining the measured mass concentrations of calcium and magnesium in the corresponding zinc solution sample based on the EDTA consumption volumes V1, V2, and V3 specifically comprises: The measured mass concentration of calcium is set as , the formula is: ； The measured mass concentration of magnesium is set as , the formula is: ； in Indicates the titer of EDTA to Ca in units of , Indicates that EDTA The titer is in , Indicates the preset first volume.

7. A system for determining the calcium and magnesium contents in a chloramine electrolytic zinc solution, characterized in that: The invention comprises a memory and a processor, wherein the memory stores a method program for determining the content of calcium and magnesium in a zinc electrolytic solution using a chloramine process, and when the method program is executed by the processor, the following steps are implemented: Obtaining a sample of zinc solution; delivering the zinc solution sample to a plurality of conical flasks according to a preset first volume, to obtain a plurality of conical flasks containing zinc solution; Divide a plurality of conical flasks containing zinc solution into three groups, namely the first group, the second group and the third group; Add the preset first combination of excipients sequentially into the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1; The step of sequentially adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain the EDTA consumption volume V1 specifically includes: Take any one Erlenmeyer flask containing zinc solution from the first group and set it as the first test Erlenmeyer flask; Adding water, potassium sodium tartrate solution, triethanolamine solution, buffer solution and acid chrome blue K-naphthol green B indicator in the preset first combination of auxiliary materials to the first test conical flask in sequence to obtain a first mixed solution; Titrate the EDTA standard solution in the preset first combination of excipients into the first mixed solution to obtain the EDTA consumption volume V (1-n) corresponding to the first test conical flask; Traverse all the conical flasks containing zinc solution in the first group and obtain the first set of EDTA consumption volume , where 1-n represents the number of the conical flask in the first group; The formula for the EDTA consumption volume V1 is: ; Also includes: Calculate the difference between each value in the first set of EDTA consumption volumes and the EDTA consumption volume V1 to obtain a first volume difference value set; Calculate the average value of the values ​​in the first volume difference value set to obtain a first volume average difference value; Divide the first volume average difference by the EDTA consumption volume V1 to obtain the first volume average difference ratio; If the first volume average difference ratio is less than or equal to a preset first volume average difference ratio threshold, the corresponding first set of EDTA consumption volumes is normal; If the first volume average difference ratio is greater than a preset first volume average difference ratio threshold, then obtaining a sample volume multiple based on the preset first range within which the first volume average difference falls; Multiplying the sample volume multiple by the preset first volume to obtain the zinc solution sample volume of the second first group, which is set as the second volume; Inputting the second volume of the zinc solution sample into a preset conical flask to obtain a conical flask containing the second volume of the zinc solution, and constructing a second first group; The preset first combination of excipients in multiples of the sample volume are sequentially added to the conical flask containing the second volume of zinc solution in the second first group to obtain the second first set of EDTA consumption volume. ,in Indicates the number of the conical flask in the first group; According to the first set of EDTA consumption volumes, the revised EDTA consumption volume V1 is obtained, which is set as , the formula is: in Indicates the sample volume multiple; Sequentially adding a preset second combination of excipients to the conical flask containing the zinc solution in the second group to obtain an EDTA consumption volume V2; the preset second group of excipients includes hydrochloric acid, ammonium fluoride, saturated thiourea solution, ascorbic acid, acetic acid-sodium acetate buffer solution and EDTA standard solution; Sequentially adding a preset third combination of excipients to the conical flask containing the zinc solution in the third group to obtain an EDTA consumption volume V3; the preset third combination of excipients includes triethanolamine solution, potassium hydroxide, calcium indicator and EDTA standard solution; According to the EDTA consumption volumes V1, V2 and V3, the measured mass concentrations of calcium and magnesium in the corresponding zinc solution samples were obtained.

8. The system for measuring calcium and magnesium contents in a chlorine-ammonia electrolytic zinc solution according to claim 7, further comprising: acquiring an image of the first mixed solution in real time; extracting color feature values ​​from the image of the first mixed solution; When the difference between the color characteristic value in the image of the first mixed solution and the preset first color characteristic value is less than the preset first color difference threshold, the titration of the corresponding EDTA standard solution is stopped.

Images