A method and system for determining ammonium chloride in electrolytic zinc solution using the chlorammonia method

Abstract

The present invention discloses a method and system for determining ammonium chloride in an electrolytic zinc solution using a chloramine process. The method comprises: obtaining a zinc solution sample; 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; dividing the plurality of conical flasks containing the zinc solution into two groups, namely a first group and a second group; adding a preset first combination of auxiliary materials to the conical flasks containing the zinc solution in the first group to obtain a consumed volume of EDTA standard solution V1; sequentially adding the EDTA standard solution with a volume of V1 and a preset second combination of auxiliary materials to the conical flasks containing the zinc solution in the second group to obtain consumed volumes of sodium hydroxide standard solution V2 and V3; and obtaining a measured molar concentration of ammonium chloride in the zinc solution sample based on the consumed volumes of sodium hydroxide standard solution V2 and V3. The present invention can improve the determination accuracy of ammonium chloride in the electrolytic zinc solution.

Description

Technical Field

[0001] The present invention relates to the field of detection technology, and more specifically to a method and system for determining ammonium chloride in a zinc electrolysis solution using a chlorammonia process. Background Art

[0002] In the past, electrolytic zinc was produced using the acid method. No ammonium chloride was produced during the production process, so there was no method to determine ammonium chloride. The results obtained by directly using the ammonium chloride determination method were very different from the actual results.

[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 ammonium chloride in electrolytic zinc solution by the chlorammonia method, which can improve the determination accuracy of ammonium chloride in electrolytic zinc solution.

[0005] A first aspect of the present invention provides a method for determining ammonium chloride in a zinc electrolysis 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 zinc solution;

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

[0009] Add the preset first combination of excipients to the conical flasks containing zinc solution in the first group respectively to obtain the volume of consumed EDTA standard solution V1;

[0010] Add V1 volume of EDTA standard solution and the preset second combination of excipients to the conical flask containing zinc solution in the second group in sequence to obtain the consumed volumes of sodium hydroxide standard solution V2 and V3;

[0011] According to the consumed volumes V2 and V3 of the sodium hydroxide standard solution, the measured molar concentration of ammonium chloride in the zinc solution sample is obtained.

[0012] In this solution, the step of adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain the volume V1 of the consumed EDTA standard solution specifically includes:

[0013] Based on a preset first ratio, hydrochloric acid, ammonium fluoride, ascorbic acid, and saturated thiourea in a preset first combination of excipients are added to the conical flask containing the zinc solution in the first group to obtain a first mixed solution, and the hexamethylenetetramine solution is titrated into the first mixed solution, and an image of the first mixed solution is acquired in real time;

[0014] extracting color features from the first mixed solution image;

[0015] Comparing and analyzing the color feature in the first mixed solution image and the preset first color feature to obtain a first similarity value;

[0016] If the first similarity value is less than the preset first similarity threshold, continue adding the hexamethylenetetramine solution to the first mixed solution;

[0017] If the first similarity value is greater than or equal to a preset first similarity threshold, then adding a preset second volume of hexamethylenetetramine solution to the first mixed solution to obtain a second mixed solution;

[0018] Inputting the EDTA standard solution in the preset first combination excipient into the second mixed solution, and acquiring the corresponding image of the second mixed solution in real time;

[0019] extracting color features from the second mixed solution image;

[0020] Comparing and analyzing the color feature in the second mixed solution image with the preset second color feature to obtain a second similarity value;

[0021] If the second similarity value is greater than or equal to the preset second similarity threshold, the titration of the EDTA standard solution is stopped, and the volume V(1-n) of the EDTA standard solution consumed by the second mixed solution in the corresponding numbered conical flask is recorded;

[0022] Traverse all the Erlenmeyer flasks containing zinc solution in the first group to obtain the volume set of EDTA standard solution consumed by the second mixed solution {V(1-1), V(1-2), …, V(1-n)}, where n represents the number of the Erlenmeyer flask containing zinc solution in the first group and is a positive integer;

[0023] The volume of consumed EDTA standard solution is set as V1, and the formula is:

[0024] This plan also includes:

[0025] When the second similarity value is greater than or equal to the preset second value, subtracting the preset second value from the second similarity value to obtain a second similarity difference;

[0026] Multiplying the second similarity difference by a preset time interval base to obtain a time interval increase value;

[0027] The time interval increase value and the titration interval of the EDTA standard solution are accumulated to obtain the revised titration interval of the EDTA standard solution;

[0028] Based on the revised titration interval of the EDTA standard solution, the second mixed solution is titrated with the EDTA standard solution.

[0029] This plan also includes:

[0030] Determining a level corresponding to the second similarity difference value according to the preset similarity difference range within which the second similarity difference value falls;

[0031] According to the level of the second similarity difference, matching the burette of corresponding specifications;

[0032] The EDTA standard solution is titrated against the second mixed solution using a burette of corresponding grade.

[0033] This plan also includes:

[0034] performing a difference calculation between any volume V(1-n) in the volume set of the EDTA standard solution consumed by extracting the second mixed solution and the volume V1 of the consumed EDTA standard solution to obtain a first volume difference;

[0035] If the first volume difference is greater than a preset first volume difference threshold, V(1-n) corresponding to the first volume difference is deleted to obtain a revised volume set of EDTA standard solution consumed by the second mixed solution;

[0036] The consumed EDTA standard solution volume V1 is recalculated based on the revised EDTA standard solution volume set consumed by the second mixed solution until the difference between any volume V(1-n) in the EDTA standard solution volume set consumed by the second mixed solution and the consumed EDTA standard solution volume V1 is less than or equal to the preset first volume difference threshold.

[0037] In this solution, the step of sequentially adding a volume of V1 of EDTA standard solution and a preset second combination of excipients to the conical flask containing zinc solution in the second group to obtain the consumed volumes V2 and V3 of sodium hydroxide standard solution specifically includes:

[0038] Add V1 volume of EDTA standard solution to the conical flask containing zinc solution in the second group, and then add a third volume of methyl red-methylene blue mixed indicator preset in the preset second combination auxiliary to obtain a third mixed solution;

[0039] titrating the sodium hydroxide standard solution in the preset second combination auxiliary material into the third mixed solution, and acquiring an image of the third mixed solution in real time;

[0040] extracting color features from the third mixed solution image;

[0041] Comparing and analyzing the color feature in the third mixed solution image and the preset third color feature to obtain a third similarity value;

[0042] If the third similarity value is greater than the preset third similarity threshold, the titration of the sodium hydroxide standard solution is stopped, and the volume V(2-m) of the sodium hydroxide standard solution consumed by the third mixed solution in the corresponding numbered conical flask is recorded;

[0043] Based on the preset second ratio, the formaldehyde solution and the phenolphthalein indicator in the preset second combination of auxiliary materials are added to the third mixed solution to obtain a fourth mixed solution;

[0044] titrating the sodium hydroxide standard solution in the preset second combination auxiliary material into the fourth mixed solution, and acquiring an image of the fourth mixed solution in real time;

[0045] extracting color features from the fourth mixed solution image;

[0046] Comparing and analyzing the color feature in the fourth mixed solution image with the preset fourth color feature to obtain a fourth similarity value;

[0047] If the fourth similarity value is greater than the preset fourth similarity threshold, the titration of the sodium hydroxide standard solution is stopped, and the volume V(3-m) of the sodium hydroxide standard solution consumed by the fourth mixed solution in the corresponding numbered conical flask is recorded;

[0048] Traversing the entire conical flask containing zinc solution in the second group, the combination set of the volume of sodium hydroxide standard solution consumed in the third mixed solution and the fourth mixed solution is:

[0049] {V(2-1), V(3-1); V(2-2), V(3-2); ...; V(2-m), V(3-m)}, where m represents the number of the conical flask containing the zinc solution in the second group, and m is a positive integer;

[0050] Consumed volume of sodium hydroxide standard solution

[0051] Consumed volume of sodium hydroxide standard solution

[0052] In this solution, the formula for determining the molar concentration of ammonium chloride in the zinc solution sample based on the consumed volumes V2 and V3 of the sodium hydroxide standard solution is specifically:

[0053]

[0054] Among them C NH4Cl Expressed as the measured molar concentration of ammonium chloride; C NaOH represents the molar concentration of the sodium hydroxide standard solution; V0 represents the preset first volume; 53.5 is the molar mass of NH4Cl, in g / mol.

[0055] A second aspect of the present invention provides a system for determining ammonium chloride in a zinc solution electrolyzed by ammonia chlorine method, comprising a memory and a processor. The memory stores a program for determining ammonium chloride in a zinc solution electrolyzed by ammonia chlorine method. When the program is executed by the processor, the following steps are implemented:

[0056] Obtaining a sample of zinc solution;

[0057] 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;

[0058] Divide a plurality of conical flasks containing zinc solution into two groups, namely the first group and the second group;

[0059] Add the preset first combination of excipients to the conical flasks containing zinc solution in the first group respectively to obtain the volume of consumed EDTA standard solution V1;

[0060] Add V1 volume of EDTA standard solution and the preset second combination of excipients to the conical flask containing zinc solution in the second group in sequence to obtain the consumed volumes of sodium hydroxide standard solution V2 and V3;

[0061] According to the consumed volumes V2 and V3 of the sodium hydroxide standard solution, the measured molar concentration of ammonium chloride in the zinc solution sample is obtained.

[0062] In this solution, the step of adding the preset first combination of excipients to the conical flask containing the zinc solution in the first group to obtain the volume V1 of the consumed EDTA standard solution specifically includes:

[0063] Based on a preset first ratio, hydrochloric acid, ammonium fluoride, ascorbic acid, and saturated thiourea in a preset first combination of excipients are added to the conical flask containing the zinc solution in the first group to obtain a first mixed solution, and the hexamethylenetetramine solution is titrated into the first mixed solution, and an image of the first mixed solution is acquired in real time;

[0064] extracting color features from the first mixed solution image;

[0065] Comparing and analyzing the color feature in the first mixed solution image and the preset first color feature to obtain a first similarity value;

[0066] If the first similarity value is less than the preset first similarity threshold, continue adding the hexamethylenetetramine solution to the first mixed solution;

[0067] If the first similarity value is greater than or equal to a preset first similarity threshold, then adding a preset second volume of hexamethylenetetramine solution to the first mixed solution to obtain a second mixed solution;

[0068] Inputting the EDTA standard solution in the preset first combination excipient into the second mixed solution, and acquiring the corresponding image of the second mixed solution in real time;

[0069] extracting color features from the second mixed solution image;

[0070] Comparing and analyzing the color feature in the second mixed solution image with the preset second color feature to obtain a second similarity value;

[0071] If the second similarity value is greater than or equal to the preset second similarity threshold, the titration of the EDTA standard solution is stopped, and the volume V(1-n) of the EDTA standard solution consumed by the second mixed solution in the corresponding numbered conical flask is recorded;

[0072] Traverse all the Erlenmeyer flasks containing zinc solution in the first group to obtain the volume set of EDTA standard solution consumed by the second mixed solution {V(1-1), V(1-2), …, V(1-n)}, where n represents the number of the Erlenmeyer flask containing zinc solution in the first group and is a positive integer;

[0073] The volume of consumed EDTA standard solution is set as V1, and the formula is:

[0074] This plan also includes:

[0075] When the second similarity value is greater than or equal to the preset second value, subtracting the preset second value from the second similarity value to obtain a second similarity difference;

[0076] Multiplying the second similarity difference by a preset time interval base to obtain a time interval increase value;

[0077] The time interval increase value and the titration interval of the EDTA standard solution are accumulated to obtain the revised titration interval of the EDTA standard solution;

[0078] Based on the revised titration interval of the EDTA standard solution, the second mixed solution is titrated with the EDTA standard solution.

[0079] The invention discloses a method and system for determining ammonium chloride in an electrolytic zinc solution using a chloramine process, which can improve the determination accuracy of ammonium chloride in the electrolytic zinc solution. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 A flow chart showing a method for determining ammonium chloride in a zinc electrolytic solution using the chloramine method of the present invention is provided;

[0081] Figure 2 The block diagram of the system for determining ammonium chloride in zinc electrolysis solution using the chlorammonia method of the present invention is shown. DETAILED DESCRIPTION

[0082] 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.

[0083] 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.

[0084] Figure 1 The present invention shows a flow chart of a method for determining ammonium chloride in a zinc electrolytic solution using the chloramine method.

[0085] S101, obtaining a zinc solution sample;

[0086] 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;

[0087] S103, dividing the plurality of conical flasks containing zinc solution into two groups, namely a first group and a second group;

[0088] S104, adding the preset first combination of excipients to the conical flasks containing the zinc solution in the first group respectively to obtain a volume V1 of the consumed EDTA standard solution;

[0089] S105, adding V1 volume of EDTA standard solution and the preset second combination of excipients to the conical flask containing zinc solution in the second group in sequence, to obtain consumed volumes V2 and V3 of sodium hydroxide standard solution;

[0090] S106, obtaining the measured molar concentration of ammonium chloride in the zinc solution sample based on the consumed volumes V2 and V3 of the sodium hydroxide standard solution.

[0091] According to an embodiment of the present invention, the conical flasks containing zinc solution in the first and second groups are numbered n and m, respectively. The conical flasks are transparent, and the color change of the solution in the conical flask can be directly observed from the outside. After a preset first volume of the zinc solution sample is loaded into each conical flask, it needs to be diluted with water according to a set ratio. For example, if the dilution ratio is set to 100, then when the preset first volume is 1 milliliter, the zinc solution in the conical flask needs to be diluted with water to 100 milliliters. If the preset first volume is 2 milliliters, the zinc solution in the conical flask needs to be diluted with water to 200 milliliters, and so on.

[0092] According to an embodiment of the present invention, the step of adding the preset first combination excipients to the conical flasks containing the zinc solution in the first group to obtain the consumed EDTA standard solution volume V1 specifically includes:

[0093] Based on a preset first ratio, hydrochloric acid, ammonium fluoride, ascorbic acid, and saturated thiourea in a preset first combination of excipients are added to the conical flask containing the zinc solution in the first group to obtain a first mixed solution, and the hexamethylenetetramine solution is titrated into the first mixed solution, and an image of the first mixed solution is acquired in real time;

[0094] extracting color features from the first mixed solution image;

[0095] Comparing and analyzing the color feature in the first mixed solution image and the preset first color feature to obtain a first similarity value;

[0096] If the first similarity value is less than the preset first similarity threshold, continue adding the hexamethylenetetramine solution to the first mixed solution;

[0097] If the first similarity value is greater than or equal to a preset first similarity threshold, then adding a preset second volume of hexamethylenetetramine solution to the first mixed solution to obtain a second mixed solution;

[0098] Inputting the EDTA standard solution in the preset first combination excipient into the second mixed solution, and acquiring the corresponding image of the second mixed solution in real time;

[0099] extracting color features from the second mixed solution image;

[0100] Comparing and analyzing the color feature in the second mixed solution image with the preset second color feature to obtain a second similarity value;

[0101] If the second similarity value is greater than or equal to the preset second similarity threshold, the titration of the EDTA standard solution is stopped, and the volume V(1-n) of the EDTA standard solution consumed by the second mixed solution in the corresponding numbered conical flask is recorded;

[0102] Traverse all the Erlenmeyer flasks containing zinc solution in the first group to obtain the volume set of EDTA standard solution consumed by the second mixed solution {V(1-1), V(1-2), …, V(1-n)}, where n represents the number of the Erlenmeyer flask containing zinc solution in the first group and is a positive integer;

[0103] The volume of consumed EDTA standard solution is set as V1, and the formula is:

[0104] It should be noted that the preset first combination of auxiliary materials includes: hydrochloric acid, ammonium fluoride, ascorbic acid, saturated thiourea, hexamethylenetetramine solution and EDTA standard solution. In this embodiment, taking 1 ml of zinc solution test as an example, 1 ml of zinc solution sample is placed in a transparent conical flask, and then water is added to 100 ml, 2 to 3 ml of 1:1 hydrochloric acid, 0.2 g of ammonium fluoride, 0.2 g of ascorbic acid, 10 ml of saturated thiourea, and shaken to obtain a first mixed solution, and then the hexamethylenetetramine solution is titrated to the first mixed solution until the first mixed solution becomes a purple-red corresponding to the preset first color feature, and then a preset second volume of hexamethylenetetramine solution is added in excess, for example, 5 ml in excess, and then the EDTA standard solution is used. The liquid is titrated until the preset second color characteristic corresponding to bright yellow is obtained, and the volume of the EDTA standard solution consumed by the second mixed solution in the corresponding numbered conical flask is recorded; when the extracted zinc solution sample increases or decreases in proportion, the excipients in the corresponding preset first combination of excipients are increased or decreased in proportion. For example, taking a 2 ml zinc solution test as an example, 2 ml of the zinc solution sample is placed in a transparent conical flask, and then water is added to 200 ml. 4 to 6 ml of 1:1 hydrochloric acid, 0.4 g of ammonium fluoride, 0.4 g of ascorbic acid, and 20 ml of saturated thiourea are added and shaken to obtain a first mixed solution. Similarly, the saturated thiourea is a saturated solution aqueous solution; the preset first ratio is the ratio of the zinc solution sample and the preset first combination of excipients.

[0105] According to an embodiment of the present invention, the further embodiment includes:

[0106] When the second similarity value is greater than or equal to the preset second value, subtracting the preset second value from the second similarity value to obtain a second similarity difference;

[0107] Multiplying the second similarity difference by a preset time interval base to obtain a time interval increase value; accumulating the time interval increase value and the titration interval of the EDTA standard solution to obtain a revised titration interval of the EDTA standard solution;

[0108] Based on the revised titration interval of the EDTA standard solution, the second mixed solution is titrated with the EDTA standard solution.

[0109] It should be noted that the preset second numerical value is less than the preset second similarity threshold and greater than zero. When the second similarity difference is larger, the second similarity value corresponding to the second similarity difference is closer to the preset second similarity threshold, and the titration interval of the EDTA standard solution is larger, giving sufficient reaction time for the second mixed solution to reduce errors. The preset time interval base is a number greater than zero.

[0110] According to an embodiment of the present invention, the further embodiment includes:

[0111] Determining a level corresponding to the second similarity difference value according to the preset similarity difference range within which the second similarity difference value falls;

[0112] According to the level of the second similarity difference, matching the burette of corresponding specifications;

[0113] The EDTA standard solution is titrated against the second mixed solution using a burette of corresponding grade.

[0114] It should be noted that the volume of each titration corresponding to different burette specifications is different, wherein the larger the burette specification, the larger the volume of each titration. For example, if the preset similarity difference range is divided into intervals of 5%, the preset similarity difference range can be divided into: (0%, 5%], (5%, 10%], ..., and so on; wherein the larger the value in the preset similarity difference range, the higher the level of the corresponding second similarity difference value, wherein each level of the second similarity difference value corresponds to a burette specification, and the higher the level of the second similarity difference, the smaller the corresponding burette specification.

[0115] According to an embodiment of the present invention, the further embodiment includes:

[0116] performing a difference calculation between any volume V(1-n) in the volume set of the EDTA standard solution consumed by extracting the second mixed solution and the volume V1 of the consumed EDTA standard solution to obtain a first volume difference;

[0117] If the first volume difference is greater than a preset first volume difference threshold, V(1-n) corresponding to the first volume difference is deleted to obtain a revised volume set of EDTA standard solution consumed by the second mixed solution;

[0118] The consumed EDTA standard solution volume V1 is recalculated based on the revised EDTA standard solution volume set consumed by the second mixed solution until the difference between any volume V(1-n) in the EDTA standard solution volume set consumed by the second mixed solution and the consumed EDTA standard solution volume V1 is less than or equal to the preset first volume difference threshold.

[0119] It should be noted that, by presetting the first volume difference threshold to determine the first volume difference, individual experimental errors are eliminated, and the accuracy of the consumed EDTA standard solution volume V1 is improved.

[0120] According to an embodiment of the present invention, the step of sequentially adding a volume of V1 of EDTA standard solution and a preset second combination excipient to the conical flask containing zinc solution in the second group to obtain the consumed volumes V2 and V3 of sodium hydroxide standard solution specifically includes:

[0121] Add V1 volume of EDTA standard solution to the conical flask containing zinc solution in the second group, and then add a third volume of methyl red-methylene blue mixed indicator preset in the preset second combination auxiliary to obtain a third mixed solution;

[0122] titrating the sodium hydroxide standard solution in the preset second combination auxiliary material into the third mixed solution, and acquiring an image of the third mixed solution in real time;

[0123] extracting color features from the third mixed solution image;

[0124] Comparing and analyzing the color feature in the third mixed solution image and the preset third color feature to obtain a third similarity value;

[0125] If the third similarity value is greater than the preset third similarity threshold, the titration of the sodium hydroxide standard solution is stopped, and the volume V(2-m) of the sodium hydroxide standard solution consumed by the third mixed solution in the corresponding numbered conical flask is recorded;

[0126] Based on the preset second ratio, the formaldehyde solution and the phenolphthalein indicator in the preset second combination of auxiliary materials are added to the third mixed solution to obtain a fourth mixed solution;

[0127] titrating the sodium hydroxide standard solution in the preset second combination auxiliary material into the fourth mixed solution, and acquiring an image of the fourth mixed solution in real time;

[0128] extracting color features from the fourth mixed solution image;

[0129] Comparing and analyzing the color feature in the fourth mixed solution image with the preset fourth color feature to obtain a fourth similarity value;

[0130] If the fourth similarity value is greater than the preset fourth similarity threshold, the titration of the sodium hydroxide standard solution is stopped, and the volume V(3-m) of the sodium hydroxide standard solution consumed by the fourth mixed solution in the corresponding numbered conical flask is recorded;

[0131] Traversing the entire conical flask containing zinc solution in the second group, the combination set of the volume of sodium hydroxide standard solution consumed in the third mixed solution and the fourth mixed solution is:

[0132] {V(2-1), V(3-1); V(2-2), V(3-2); ...; V(2-m), V(3-m)}, where m represents the number of the conical flask containing the zinc solution in the second group, and m is a positive integer;

[0133] Consumed volume of sodium hydroxide standard solution

[0134] Consumed volume of sodium hydroxide standard solution

[0135] It should be noted that the preset second combination of auxiliary materials includes: EDTA standard solution, methyl red-methylene blue mixed indicator, sodium hydroxide standard solution, formaldehyde solution and phenolphthalein indicator. In this embodiment, taking 1 ml of zinc solution test as an example, 1 ml of zinc solution sample is placed in a transparent conical flask, and then water is added to 100 ml, and then V1 volume of EDTA standard solution is added, and 1 to 2 ml of methyl red-methylene blue mixed indicator are added to obtain a third mixed solution, which is then titrated with sodium hydroxide standard solution until the purple-red color disappears, and the sodium oxide standard solution consumed by the third mixed solution in the corresponding numbered conical flask is recorded. volume; then add 10 ml of neutral formaldehyde solution and 1.5 to 2.5 ml of phenolphthalein indicator, continue to titrate with sodium hydroxide standard solution until the purple-red color does not fade, corresponding to the preset fourth color characteristic, and continue for a preset time, such as 30 seconds, and then record the volume of sodium hydroxide standard solution consumed by the fourth mixed solution in the corresponding numbered conical flask; when the extracted zinc solution sample increases or decreases according to the proportion, the EDTA standard solution, methyl red-methylene blue mixed indicator, neutral formaldehyde solution and phenolphthalein indicator in the preset second combination of auxiliary materials are all increased or decreased according to the corresponding proportion; the preset second proportion is the ratio of the preset second combination of auxiliary materials and the zinc solution sample.

[0136] Furthermore, when the sodium hydroxide standard solution is used to titrate the third mixed solution and the fourth mixed solution, a third numerical value and a fourth numerical value are set respectively, and the third numerical value is less than a preset third similarity threshold value and greater than zero, and the fourth numerical value is less than a preset fourth similarity threshold value and greater than zero. When the third similarity value is greater than the third numerical value, the third numerical value is subtracted from the third similarity value to obtain a third similarity difference, and according to the preset third similarity difference range within which the third similarity difference falls, the level corresponding to the third similarity difference is determined, and the burette of the corresponding specification is matched according to the level of the third similarity difference. Similarly, the burette of the corresponding specification is matched according to the preset fourth similarity difference range within which the fourth similarity difference falls. The principle steps of matching the titration speed of the sodium hydroxide standard solution and the corresponding burette specifications are the same as the principle steps of matching the titration speed of the EDTA standard solution and the corresponding burette specifications.

[0137] Furthermore, after calculating the consumed volumes V2 and V3 of the standard sodium hydroxide solution, the difference between any V(2-m) and V2 in the combination set of the volumes of the standard sodium hydroxide solution consumed in the third mixed solution and the fourth mixed solution is calculated, and the absolute value is taken to obtain a second volume difference; the difference between any V(3-m) and V3 in the combination set of the volumes of the standard sodium hydroxide solution consumed in the third mixed solution and the fourth mixed solution is calculated, and the absolute value is taken to obtain a third volume difference; if the second volume difference of the same number is greater than the preset second volume difference threshold or the third volume difference is greater than the preset third volume difference threshold, the corresponding numbered V(2-m) and V(3-m) are deleted at the same time, and V2 and V3 are recalculated until the second volume difference between any V(2-m) and V2 in the combination set of the volumes of the standard sodium hydroxide solution consumed in the third mixed solution and the fourth mixed solution is less than or equal to the preset second volume difference threshold and the third volume difference between V(3-m) and V3 is less than or equal to the preset third volume difference threshold.

[0138] According to an embodiment of the present invention, the formula for determining the molar concentration of ammonium chloride in the zinc solution sample based on the consumed volumes V2 and V3 of the sodium hydroxide standard solution is specifically:

[0139]

[0140] in Expressed as the measured molar concentration of ammonium chloride; C NaOH represents the molar concentration of the sodium hydroxide standard solution; V0 represents the preset first volume; 53.5 is the molar mass of NH4Cl, in g / mol.

[0141] Figure 2 The block diagram of the system for determining ammonium chloride in zinc electrolysis solution using the chlorammonia method of the present invention is shown.

[0142] like Figure 2 As shown, the second aspect of the present invention provides a system 2 for determining ammonium chloride in a zinc solution electrolyzed by ammonia chlorine method, comprising a memory 21 and a processor 22. The memory stores a program for determining ammonium chloride in a zinc solution electrolyzed by ammonia chlorine method. When the program is executed by the processor, the following steps are implemented:

[0143] Obtaining a sample of zinc solution;

[0144] 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;

[0145] Divide a plurality of conical flasks containing zinc solution into two groups, namely a first group and a second group, and number the conical flasks containing zinc solution in the first group and the second group, namely n and m, respectively;

[0146] Add the preset first combination of excipients to the conical flasks containing zinc solution in the first group respectively to obtain the volume of consumed EDTA standard solution V1;

[0147] Add V1 volume of EDTA standard solution and the preset second combination of excipients to the conical flask containing zinc solution in the second group in sequence to obtain the consumed volumes of sodium hydroxide standard solution V2 and V3;

[0148] According to the consumed volumes V2 and V3 of the sodium hydroxide standard solution, the measured molar concentration of ammonium chloride in the zinc solution sample is obtained.

[0149] According to an embodiment of the present invention, the step of adding the preset first combination excipients to the conical flasks containing the zinc solution in the first group to obtain the consumed EDTA standard solution volume V1 specifically includes:

[0150] Based on a preset first ratio, hydrochloric acid, ammonium fluoride, ascorbic acid, saturated thiourea, and hexamethylenetetramine solution in the preset first combination of excipients are sequentially added to the conical flask containing the zinc solution in the first group to obtain a first mixed solution, and an image of the first mixed solution is extracted;

[0151] extracting color features from the first mixed solution image;

[0152] Comparing and analyzing the color feature in the first mixed solution image and the preset first color feature to obtain a first similarity value;

[0153] If the first similarity value is less than the preset first similarity threshold, continue adding the hexamethylenetetramine solution to the first mixed solution;

[0154] If the first similarity value is greater than or equal to a preset first similarity threshold, then adding a preset second volume of hexamethylenetetramine solution to the first mixed solution to obtain a second mixed solution;

[0155] Inputting the EDTA standard solution in the preset first combination excipient into the second mixed solution, and acquiring the corresponding image of the second mixed solution in real time;

[0156] extracting color features from the second mixed solution image;

[0157] Comparing and analyzing the color feature in the second mixed solution image with the preset second color feature to obtain a second similarity value;

[0158] If the second similarity value is greater than or equal to the preset second similarity threshold, the titration of the EDTA standard solution is stopped, and the volume V(1-n) of the EDTA standard solution consumed by the second mixed solution in the corresponding numbered conical flask is recorded;

[0159] Traverse all the Erlenmeyer flasks containing zinc solution in the first group to obtain the volume set of EDTA standard solution consumed by the second mixed solution {V(1-1), V(1-2), …, V(1-n)}, where n represents the number of the Erlenmeyer flask containing zinc solution in the first group and is a positive integer;

[0160] The volume of consumed EDTA standard solution is set as V1, and the formula is:

[0161] According to an embodiment of the present invention, the further embodiment includes:

[0162] When the second similarity value is greater than or equal to the preset second value, subtracting the preset second value from the second similarity value to obtain a second similarity difference;

[0163] Multiplying the second similarity difference by a preset time interval base to obtain a time interval increase value;

[0164] The time interval increase value and the titration interval of the EDTA standard solution are accumulated to obtain the revised titration interval of the EDTA standard solution;

[0165] Based on the revised titration interval of the EDTA standard solution, the second mixed solution is titrated with the EDTA standard solution.

[0166] The invention discloses a method and system for determining ammonium chloride in an electrolytic zinc solution using a chloramine process, which can improve the determination accuracy of ammonium chloride in the electrolytic zinc solution.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] 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 ammonium chloride in a chloramine electrolytic zinc solution, characterized in that: include: 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 two groups, namely the first group and the second group; Add the preset first combination of excipients to the conical flasks containing zinc solution in the first group respectively to obtain the volume V1 of the consumed EDTA standard solution; The preset first combination of auxiliary materials includes: hydrochloric acid, ammonium fluoride, ascorbic acid, saturated thiourea, hexamethylenetetramine solution and EDTA standard solution; Based on a preset first ratio, hydrochloric acid, ammonium fluoride, ascorbic acid and saturated thiourea in the preset first combination of auxiliary materials are added to the conical flask containing the zinc solution in the first group to obtain a first mixed solution, and then the hexamethylenetetramine solution is titrated into the first mixed solution until the first mixed solution turns into a preset first color characteristic corresponding to purple-red, and then a preset second volume of hexamethylenetetramine solution is added in excess to obtain a second mixed solution, and then the EDTA standard solution is titrated until the preset second color characteristic corresponding to bright yellow is obtained, and the volume of EDTA standard solution consumed by the second mixed solution in the corresponding numbered conical flask is recorded. , traverse the entire conical flask containing zinc solution in the first group, and obtain the volume set of EDTA standard solution consumed by the second mixed solution , n represents the number of the conical flask containing zinc solution in the first group, n is a positive integer, and the volume of the consumed EDTA standard solution is set to V1, and the formula is: ; Sequentially adding a volume of V1 of EDTA standard solution and a preset second combination of excipients to the conical flask containing the zinc solution in the second group to obtain consumed volumes V2 and V3 of the sodium hydroxide standard solution; the preset second combination of excipients comprising: EDTA standard solution, methyl red-methylene blue mixed indicator, sodium hydroxide standard solution, formaldehyde solution, and phenolphthalein indicator; Add V1 volume of EDTA standard solution to the conical flask containing zinc solution in the second group, and then add the third volume of methyl red-methylene blue mixed indicator preset in the preset second combination of auxiliary materials to obtain a third mixed solution; then titrate with sodium hydroxide standard solution until the purple-red color disappears, corresponding to the preset third color characteristic, and record the volume of sodium oxide standard solution consumed by the third mixed solution in the corresponding numbered conical flask. Based on the preset second ratio, the formaldehyde solution and phenolphthalein indicator in the preset second combination of auxiliary materials are added to the third mixed solution to obtain a fourth mixed solution, which is titrated with a sodium hydroxide standard solution until the purple-red color does not fade, corresponding to the preset fourth color characteristic, and the color is maintained for a preset time, and then the volume of the sodium hydroxide standard solution consumed by the fourth mixed solution in the corresponding numbered conical flask is recorded. Traverse the entire second group of conical flasks containing zinc solution, and obtain the combined set of the volume of sodium hydroxide standard solution consumed in the third mixed solution and the fourth mixed solution: , m represents the number of the conical flask containing zinc solution in the second group, and m is a positive integer; Consumed volume of sodium hydroxide standard solution ; Consumed volume of sodium hydroxide standard solution ; According to the consumed volumes V2 and V3 of the sodium hydroxide standard solution, the measured molar concentration of ammonium chloride in the zinc solution sample is obtained.

2. The method for determining ammonium chloride in a chloramine electrolytic zinc solution according to claim 1, wherein: The step of adding the preset first combination of auxiliary materials to the conical flasks containing the zinc solution in the first group to obtain the volume V1 of the consumed EDTA standard solution specifically includes: acquiring an image of the first mixed solution in real time; extracting color features from the first mixed solution image; Comparing and analyzing the color feature in the first mixed solution image and the preset first color feature to obtain a first similarity value; If the first similarity value is less than the preset first similarity threshold, continue adding the hexamethylenetetramine solution to the first mixed solution; If the first similarity value is greater than or equal to a preset first similarity threshold, then adding a preset second volume of hexamethylenetetramine solution to the first mixed solution to obtain a second mixed solution; Inputting the EDTA standard solution in the preset first combination excipient into the second mixed solution, and acquiring the corresponding image of the second mixed solution in real time; extracting color features from the second mixed solution image; Comparing and analyzing the color feature in the second mixed solution image with the preset second color feature to obtain a second similarity value; If the second similarity value is greater than or equal to the preset second similarity threshold, the titration of the EDTA standard solution is stopped.

3. The method for determining ammonium chloride in a chloramine electrolytic zinc solution according to claim 2, wherein: Also includes: When the second similarity value is greater than or equal to the preset second value, subtracting the preset second value from the second similarity value to obtain a second similarity difference; Multiplying the second similarity difference by a preset time interval base to obtain a time interval increase value; The time interval increase value and the titration interval of the EDTA standard solution are accumulated to obtain the revised titration interval of the EDTA standard solution; Based on the revised titration interval of the EDTA standard solution, titrating the second mixed solution with the EDTA standard solution; The preset second value is smaller than a preset second similarity threshold and greater than zero.

4. The method for determining ammonium chloride in a chloramine electrolytic zinc solution according to claim 3, wherein: Also includes: Determining a level corresponding to the second similarity difference value according to the preset similarity difference range within which the second similarity difference value falls; According to the level of the second similarity difference, matching the burette of corresponding specifications; The EDTA standard solution is titrated against the second mixed solution using a burette of corresponding grade.

5. The method for determining ammonium chloride in a chloramine electrolytic zinc solution according to claim 2, wherein: Also includes: Extracting any volume V(1-n) in the volume set of the EDTA standard solution consumed by the second mixed solution and performing a difference calculation with the volume V1 of the consumed EDTA standard solution to obtain a first volume difference; If the first volume difference is greater than a preset first volume difference threshold, V(1-n) corresponding to the first volume difference is deleted to obtain a revised volume set of EDTA standard solution consumed by the second mixed solution; The consumed EDTA standard solution volume V1 is recalculated based on the revised EDTA standard solution volume set consumed by the second mixed solution until the difference between any volume V(1-n) in the EDTA standard solution volume set consumed by the second mixed solution and the consumed EDTA standard solution volume V1 is less than or equal to the preset first volume difference threshold.

6. The method for determining ammonium chloride in a chloramine electrolytic zinc solution according to claim 1, wherein: The step of sequentially adding V1 volume of EDTA standard solution and a preset second combination of auxiliary materials into the conical flask containing zinc solution in the second group to obtain consumed volumes V2 and V3 of sodium hydroxide standard solution specifically comprises: acquiring an image of the third mixed solution in real time; extracting color features from the third mixed solution image; Comparing and analyzing the color feature in the third mixed solution image and the preset third color feature to obtain a third similarity value; If the third similarity value is greater than the preset third similarity threshold, the titration of the sodium hydroxide standard solution is stopped, and the volume V (2-m) of the sodium hydroxide standard solution consumed by the third mixed solution in the corresponding numbered conical flask is recorded; acquiring an image of the fourth mixed solution in real time; extracting color features from the fourth mixed solution image; Comparing and analyzing the color feature in the fourth mixed solution image with the preset fourth color feature to obtain a fourth similarity value; If the fourth similarity value is greater than the preset fourth similarity threshold, the titration of the sodium hydroxide standard solution is stopped, and the volume V (3-m) of the sodium hydroxide standard solution consumed by the fourth mixed solution in the corresponding numbered conical flask is recorded.

7. The method for determining ammonium chloride in a chlorine-ammonia electrolytic zinc solution according to claim 1, wherein: The formula for determining the molar concentration of ammonium chloride in the zinc solution sample based on the consumed volumes V2 and V3 of the sodium hydroxide standard solution is specifically: (mol / L) in Expressed as the measured molar concentration of ammonium chloride; Indicates the molar concentration of sodium hydroxide standard solution; Indicates the preset first volume; for The molar mass of an element is expressed in g / mol.

8. A system for determining ammonium chloride 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 ammonium chloride 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 two groups, namely the first group and the second group; Add the preset first combination of excipients to the conical flasks containing zinc solution in the first group respectively to obtain the volume V1 of the consumed EDTA standard solution; The preset first combination of auxiliary materials includes: hydrochloric acid, ammonium fluoride, ascorbic acid, saturated thiourea, hexamethylenetetramine solution and EDTA standard solution; Based on a preset first ratio, hydrochloric acid, ammonium fluoride, ascorbic acid and saturated thiourea in the preset first combination of auxiliary materials are added to the conical flask containing the zinc solution in the first group to obtain a first mixed solution, and then the hexamethylenetetramine solution is titrated into the first mixed solution until the first mixed solution turns into a preset first color characteristic corresponding to purple-red, and then a preset second volume of hexamethylenetetramine solution is added in excess to obtain a second mixed solution; and then the EDTA standard solution is titrated until the preset second color characteristic corresponding to bright yellow is obtained, and the volume of the EDTA standard solution consumed by the second mixed solution in the corresponding numbered conical flask is recorded. , traverse the entire conical flask containing zinc solution in the first group, and obtain the volume set of EDTA standard solution consumed by the second mixed solution , n represents the number of the conical flask containing zinc solution in the first group, n is a positive integer, and the volume of the consumed EDTA standard solution is set to V1, and the formula is: ; Sequentially adding a volume of V1 of EDTA standard solution and a preset second combination of excipients to the conical flask containing the zinc solution in the second group to obtain consumed volumes V2 and V3 of the sodium hydroxide standard solution; the preset second combination of excipients comprising: EDTA standard solution, methyl red-methylene blue mixed indicator, sodium hydroxide standard solution, formaldehyde solution, and phenolphthalein indicator; Add V1 volume of EDTA standard solution to the conical flask containing zinc solution in the second group, and then add the third volume of methyl red-methylene blue mixed indicator preset in the preset second combination of auxiliary materials to obtain a third mixed solution; then titrate with sodium hydroxide standard solution until the purple-red color disappears, corresponding to the preset third color characteristic, and record the volume of sodium oxide standard solution consumed by the third mixed solution in the corresponding numbered conical flask. Based on the preset second ratio, the formaldehyde solution and phenolphthalein indicator in the preset second combination of auxiliary materials are added to the third mixed solution to obtain a fourth mixed solution, which is titrated with a sodium hydroxide standard solution until the purple-red color does not fade, corresponding to the preset fourth color characteristic, and the color is maintained for a preset time, and then the volume of the sodium hydroxide standard solution consumed by the fourth mixed solution in the corresponding numbered conical flask is recorded. Traverse the entire second group of conical flasks containing zinc solution, and obtain the combined set of the volume of sodium hydroxide standard solution consumed in the third mixed solution and the fourth mixed solution: , m represents the number of the conical flask containing zinc solution in the second group, and m is a positive integer; Consumed volume of sodium hydroxide standard solution ; Consumed volume of sodium hydroxide standard solution ; According to the consumed volumes V2 and V3 of the sodium hydroxide standard solution, the measured molar concentration of ammonium chloride in the zinc solution sample is obtained.

9. The system for determining ammonium chloride in a chloramine electrolytic zinc solution according to claim 8, characterized in that: The step of adding the preset first combination of auxiliary materials to the conical flasks containing the zinc solution in the first group to obtain the volume V1 of the consumed EDTA standard solution specifically includes: acquiring an image of the first mixed solution in real time; extracting color features from the first mixed solution image; Comparing and analyzing the color feature in the first mixed solution image and the preset first color feature to obtain a first similarity value; If the first similarity value is less than the preset first similarity threshold, continue adding the hexamethylenetetramine solution to the first mixed solution; If the first similarity value is greater than or equal to a preset first similarity threshold, then adding a preset second volume of hexamethylenetetramine solution to the first mixed solution to obtain a second mixed solution; Inputting the EDTA standard solution in the preset first combination excipient into the second mixed solution, and acquiring the corresponding image of the second mixed solution in real time; extracting color features from the second mixed solution image; Comparing and analyzing the color feature in the second mixed solution image with the preset second color feature to obtain a second similarity value; If the second similarity value is greater than or equal to the preset second similarity threshold, the titration of the EDTA standard solution is stopped.

10. The system for determining ammonium chloride in a chloramine electrolytic zinc solution according to claim 9, characterized in that: Also includes: When the second similarity value is greater than or equal to the preset second value, subtracting the preset second value from the second similarity value to obtain a second similarity difference; Multiplying the second similarity difference by a preset time interval base to obtain a time interval increase value; The time interval increase value and the titration interval of the EDTA standard solution are accumulated to obtain the revised titration interval of the EDTA standard solution; Based on the revised titration interval of the EDTA standard solution, titrating the second mixed solution with the EDTA standard solution; The preset second value is smaller than a preset second similarity threshold and greater than zero.

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