Electrocobalt cleaning process

Abstract

The invention relates to the technical field of electrolytic cobalt, in particular to an electrolytic cobalt cleaning process for cobalt plate pickling, which comprises the following steps: selecting an adaptive pickling solution according to the type of an electrolytic cobalt material to be cleaned, cleaning a cobalt plate in a pickling tank, and acquiring cobalt plate pickling state data in the cobalt plate pickling process; the cobalt plate pickling state is recognized according to the dynamic change of the pickling state data; when the cobalt plate pickling state is abnormal, identifying the reason for the abnormal cobalt plate pickling state, and dynamically adjusting the cobalt plate pickling state data based on the reason for the abnormal cobalt plate pickling state; washing the cobalt plate, namely washing the cobalt plate subjected to acid washing, and cleaning the cobalt plate in a washing tank by adopting ultrasonic waves; the washed cobalt plate is scalded, the water temperature in a scalding tank is larger than or equal to 95 DEG C, and the scalding time ranges from 3 min to 5 min; according to the method, the cobalt plate pickling state abnormal reason is identified, and the cobalt plate pickling state data is dynamically adjusted based on the abnormal reason, so that the cobalt plate pickling effect is effectively improved.

Description

Technical Field

[0001] The invention relates to the technical field of electrolytic cobalt, and in particular to an electrolytic cobalt cleaning process. Background Art

[0002] In the electrolytic cobalt production of hydrochloric acid system and sulfuric acid system, there will be organic matter, crystals, oxides, anode mud or other impurities adsorbed or mixed on the surface of the electrolytic cobalt plate out of the tank, especially when the cobalt plate is burned, has pores, or is layered, the cleaning difficulty will increase. It is difficult to clean the surface of the cobalt plate with metallic luster by the commonly used cleaning method, resulting in some elements exceeding the YS / T255-2009, Co9995 standard, and the apparent quality of the cobalt plate cannot meet the requirements, thus affecting the sales of the product.

[0003] At present, the commonly used cleaning methods are: pickling, steam, ultrasonic, high-pressure jet cleaning, etc. Generally, a single cleaning method is used alone, which cannot achieve the required cleaning effect. In the pickling method, a single hydrochloric acid, sulfuric acid, nitric acid, etc. are used to clean the cobalt plate, resulting in failure to present normal metallic luster or excessive levels of certain elements. In addition, the cleaning liquid cannot be recycled, which increases the treatment cost of waste acid and wastewater. Based on this, the present invention proposes an electrolytic cobalt cleaning process. Summary of the invention

[0004] The object of the present invention is to provide an electro-cobalt cleaning process, which uses a three-step process of pickling, water washing and scalding to achieve efficient cleaning of cobalt plates, remove excess impurities, avoid exceeding the standards of elements such as copper, sulfur and carbon, and ensure that the indicators of various elements of the cobalt plates meet the standards. In the first step of pickling, the pickling state of the cobalt plate is identified according to the dynamic changes of the pickling state data. When the pickling state of the cobalt plate is abnormal, the cause of the abnormal pickling state of the cobalt plate is identified, and the pickling state data of the cobalt plate is dynamically adjusted based on the abnormal cause to improve the pickling effect of the cobalt plate.

[0005] The purpose of the present invention can be achieved through the following technical solutions: An electrolytic cobalt cleaning process comprises the following steps: Cobalt plate pickling: Select the appropriate pickling solution according to the type of electrolytic cobalt material to be cleaned, and clean the cobalt plate in the pickling tank; During the pickling process of the cobalt plate, the pickling state data of the cobalt plate is obtained, and the pickling state of the cobalt plate is identified according to the dynamic changes of the pickling state data; When the pickling state of the cobalt plate is abnormal, the cause of the abnormal pickling state of the cobalt plate is identified, and the pickling state data of the cobalt plate is dynamically adjusted based on the abnormal cause; Cobalt plate washing: Wash the cobalt plate after pickling with water, and use ultrasonic waves in the washing tank to clean the cobalt plate; Cobalt plate scalding: scald the cobalt plate after washing, the water temperature in the scalding tank is ≥95℃, and the scalding time is 3-5min; Air drying of cobalt plate: Use hot air to air dry the washed cobalt plate from top to bottom parallel to the direction of the cobalt plate until there is no residual stain on the surface; Cobalt plate cooling: The air-dried cobalt plate is cooled by blowing cold air sideways to the cobalt plate to reduce the surface temperature of the cobalt plate to room temperature.

[0006] As a further solution of the present invention: the pickling state data includes the pickling solution concentration and the pickling solution temperature; Divide the time from the start of cleaning to the current moment into several time nodes; Obtain the pickling solution concentration and pickling solution temperature corresponding to each time node in real-time state; A three-dimensional model with time nodes, the pickling solution concentration and the pickling solution temperature corresponding to the time nodes is established, and a real-time dynamic curve of the pickling solution during the pickling process of the cobalt plate is constructed within the three-dimensional model; Compare the real-time dynamic curve of the pickling liquid with the standard dynamic curve of the pickling liquid to obtain the deviation behavior value of the real-time dynamic curve of the pickling liquid relative to the standard dynamic curve of the pickling liquid; As a further solution of the present invention: if the pickling solution deviation behavior value is greater than or equal to the pickling solution deviation behavior threshold, it indicates that the pickling state of the cobalt plate is abnormal, and a pickling abnormality signal is generated; If the pickling solution deviation behavior value is less than the pickling solution deviation behavior threshold, it means that the pickling state of the cobalt plate is normal, and a normal pickling signal is generated.

[0007] As a further solution of the present invention: the process of obtaining the pickling liquid deviation behavior value is: At each time node, the corresponding points of the real-time dynamic curve of the pickling liquid and the standard dynamic curve of the pickling liquid are connected to obtain the pickling liquid interval line; Get the length of the pickling liquid interval line, and record it as the pickling liquid interval value; dividing the pickling liquid interval line into a pickling liquid abnormal line and a pickling liquid normal line based on the pickling liquid interval value; The pickling liquid abnormal line ratio is obtained by processing the proportion of the number of pickling liquid abnormal lines and recorded as Sx; The pickling liquid performance deviation ratio is obtained by processing the deviation degree between the pickling liquid abnormal line and the pickling liquid normal line, and is recorded as Sc; The abnormal interval value of the pickling liquid line is obtained by processing the ratio of the interval time of the pickling liquid abnormal line, and is recorded as St; By formula The pickling liquid deviation behavior value Si of the pickling liquid real-time dynamic curve relative to the pickling liquid standard dynamic curve is calculated.

[0008] As a further solution of the present invention: when the pickling abnormal signal is obtained, the time node corresponding to the pickling liquid abnormal line is recorded as the abnormal time node; Construct the data point set TNi=(Ti,Ni)of the pickling liquid concentration value and the data point set TCi=(Ti,Ci)of the pickling liquid temperature value at the abnormal time node under the real-time dynamic curve of the pickling liquid; Obtain the time point corresponding to the abnormal time node on the pickling liquid standard dynamic curve, and record it as the comparison time node; Construct the data point set tnj=(tj,nj)of the pickling solution concentration value at the comparison time node under the pickling solution standard dynamic curve and the data point set tcj=(tj,cj)of the pickling solution temperature value; The data point set TNi=(Ti,Ni)of the pickling solution concentration value at the abnormal time node and the data point set tnj=(tj,nj)of the comparison time node and the pickling solution concentration value are calculated point by point to obtain the abnormal concentration difference of the pickling solution at different abnormal time nodes; The data point set TCi=(Ti,Ci)of the pickling liquid temperature value at the abnormal time node is calculated point by point with the data point set tcj=(tj,cj)of the pickling liquid temperature value at the comparison time node to obtain the abnormal temperature difference of the pickling liquid at the abnormal time node.

[0009] As a further solution of the present invention: when the abnormal concentration difference of the pickling solution at the abnormal time node is outside the preset abnormal concentration difference range of the pickling solution, the abnormal time node is recorded as a concentration difference normal node; When the abnormal temperature difference of the pickling liquid is outside the preset abnormal temperature difference range of the pickling liquid at the abnormal time node, the abnormal time node is recorded as a temperature difference normal node; Obtain the number of nodes marked as normal concentration difference nodes and normal temperature difference nodes in the abnormal time nodes, and calculate the ratio of the obtained number to the number of abnormal time nodes to obtain the concentration-temperature anomaly correlation ratio; The concentration-temperature anomaly correlation ratio is identified to obtain the concentration-temperature anomaly correlation signal and the concentration-temperature anomaly non-correlation signal.

[0010] As a further solution of the present invention: when generating a concentration-temperature anomaly correlation signal; Obtain the pickling solution concentration value and pickling solution temperature value corresponding to each time node from the start of cleaning to the current moment during the pickling process of the cobalt plate; Construct the time-pickling solution concentration curve and time-pickling solution temperature curve corresponding to the time node; In the coordinate system, the time-pickling solution concentration curve and the pickling solution concentration standard local curve are processed to obtain the concentration difference to be adjusted corresponding to the time-pickling solution concentration curve; In the coordinate system, the time-pickling solution temperature curve and the pickling solution temperature standard local curve are processed to obtain the temperature difference to be adjusted corresponding to the time-pickling solution concentration curve.

[0011] As a further solution of the present invention: if the concentration difference to be adjusted is greater than zero and the temperature difference to be adjusted is greater than zero, the temperature of the pickling solution is lowered according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration-temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The adjusted concentration margin of the pickling solution and the concentration difference to be adjusted are summed to obtain the reduction in the concentration of the pickling solution; If the concentration difference to be adjusted is greater than zero and the temperature difference to be adjusted is less than zero, the temperature of the pickling solution is increased according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration-temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The difference between the adjusted concentration margin of the pickling solution and the concentration difference to be adjusted is calculated to obtain the reduction in the concentration of the pickling solution.

[0012] As a further solution of the present invention: if the concentration difference to be adjusted is less than zero and the temperature difference to be adjusted is greater than zero, the temperature of the pickling solution is lowered according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration-temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The difference between the adjusted concentration margin of the pickling solution and the concentration difference to be adjusted is calculated to obtain the increase in the concentration of the pickling solution; If the concentration difference to be adjusted is less than zero and the temperature difference to be adjusted is less than zero, the temperature of the pickling solution is increased according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration-temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The increase in the concentration of the pickling solution is calculated by summing up the adjusted concentration margin of the pickling solution and the concentration difference to be adjusted.

[0013] As a further solution of the present invention: the process of obtaining the concentration temperature adjustment ratio is: The abnormal time nodes that are marked as both the concentration difference normal node and the temperature difference normal node are recorded as the same and different time nodes; The pickling solution temperature corresponding to the maximum temperature at the same or different time nodes is recorded as Cmax, and the pickling solution concentration is recorded as Nci; The pickling solution temperature corresponding to the minimum temperature in the same and different time nodes is recorded as Cmin, and the pickling solution concentration is recorded as Nca; The concentration-temperature adjustment ratio is obtained according to the temperature change and concentration change corresponding to the maximum temperature and the minimum temperature at the same and different time nodes.

[0014] Beneficial effects of the present invention: (1) Compared with a single cleaning method, the present invention uses a three-step process of pickling, water washing and scalding, which can achieve efficient cleaning of the cobalt plate, remove excess impurities, avoid excessive levels of copper, sulfur, carbon and other elements, and ensure that the indicators of each element of the cobalt plate meet the standards. In the first pickling method, boric acid and hydrochloric acid or boric acid and sulfuric acid are used for cleaning. Compared with only one acid for cleaning, the cobalt plate surface has a clear metallic luster and enhanced surface oxidation resistance under the condition of controlling the ratio and rinsing time. In the first pickling process, the pickling state of the cobalt plate is identified according to the dynamic change of the pickling state data. When the pickling state of the cobalt plate is abnormal, the cause of the abnormal pickling state of the cobalt plate is identified, and the pickling state data of the cobalt plate is dynamically adjusted based on the abnormal cause, thereby improving the pickling effect of the cobalt plate. (2) In the pickling process of the cobalt plate, the present invention divides the current cleaning time of the cobalt plate into several time nodes, and constructs a real-time dynamic curve of the pickling solution according to the pickling solution concentration and the pickling solution temperature corresponding to the time nodes, compares the real-time dynamic curve of the pickling solution with the standard dynamic curve of the pickling solution, and obtains the degree of deviation of the real-time dynamic curve of the pickling solution compared with the standard dynamic curve of the pickling solution, thereby completing the identification of the pickling effect during the pickling process of the cobalt plate; (3) When the pickling process of the cobalt plate is abnormal, the present invention identifies the cause of the abnormal state of the pickling solution during the pickling process, performs point-to-point difference calculation on the data point set TNi=(Ti,Ni) of the pickling solution concentration value at the abnormal time node and the data point set tnj=(tj,nj) of the comparison time node and the pickling solution concentration value, and obtains the concentration difference constant node, performs point-to-point difference calculation on the data point set TCi=(Ti,Ci) of the pickling solution temperature value at the abnormal time node and the data point set tcj=(tj,cj) of the pickling solution temperature value at the comparison time node, and obtains the temperature difference constant node, and obtains the concentration-temperature abnormal correlation ratio based on the concentration difference constant node and the temperature difference constant node, thereby completing the correlation identification of the factors causing the abnormality in the pickling process; (4) When the concentration-temperature anomaly correlation signal is generated, the present invention constructs a time-pickling solution concentration curve and a time-pickling solution temperature curve corresponding to the time node, processes the time-pickling solution concentration curve to obtain the corresponding concentration difference to be adjusted, and processes the time-pickling solution concentration curve to obtain the corresponding temperature difference to be adjusted. In the adjustment process of the concentration difference to be adjusted and the temperature difference to be adjusted, the concentration-temperature adjustment ratio is integrated to complete the subsequent dynamic adjustment of the concentration and temperature of the pickling solution, and the adjustment accuracy is high. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The present invention will be further described below in conjunction with the accompanying drawings.

[0016] Figure 1 This is a flow chart of an electrolytic cobalt cleaning process according to an embodiment of the present invention; Figure 2 is a flowchart of an electrolytic cobalt cleaning process according to an embodiment of the present invention; Figure 3 The invention relates to a cobalt plate having metallic luster obtained after cleaning by an electro-cobalt cleaning process in an embodiment of the invention. DETAILED DESCRIPTION

[0017] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] Example 1 See also Figure 1-Figure 3 As shown, the present invention is an electrolytic cobalt cleaning process, comprising the following steps: Cobalt plate pickling: Select the appropriate pickling solution according to the type of electrolytic cobalt material to be cleaned, and clean the cobalt plate in the pickling tank; When the type of electrolytic cobalt material is cobalt chloride system, the pickling solution used is hydrochloric acid + boric acid, with a hydrochloric acid concentration of 10-15% and a boric acid concentration of 3-6%, and the soaking time is 20-40 minutes; When the type of electrolytic cobalt material is cobalt sulfate system, the pickling solution used is sulfuric acid + boric acid, the sulfuric acid concentration is 15-25%, the boric acid concentration is 2-4%, and the soaking time is 3-5 minutes; Cobalt plate washing: Wash the cobalt plate after pickling with water, and use ultrasonic waves in the washing tank to clean the cobalt plate; Among them, the water washing time is 3-5min; Cobalt plate scalding: scald the cobalt plate after washing, the water temperature in the scalding tank is ≥95℃, and the scalding time is 3-5min; Air drying of cobalt plate: Use hot air to air dry the washed cobalt plate from top to bottom parallel to the direction of the cobalt plate until there is no residual stain on the surface; Among them, the wind pressure is 50-80Kpa, the air outlet temperature is normal temperature -350℃, and the air volume is 800-1000m 3 / h hot air; Cobalt plate cooling: Use cold air to cool the air-dried cobalt plate sideways to reduce the surface temperature of the cobalt plate to room temperature; Among them, the wind pressure is 200-300pa, the air outlet temperature is 20-28℃, and the air volume is 1200-2000m 3 / h of cold wind.

[0019] In a specific embodiment, the cobalt plates are arranged vertically and equidistantly in a special hanging basket, and the cobalt plates are completely immersed in the pickling solution. After the pickling time reaches the requirement, the cobalt plates enter the pickling tank for water washing after the acid is fully controlled.

[0020] In a specific embodiment, during the pickling process of the cobalt plate, when the cobalt concentration of the pickling solution is ≥30 g / l, it is returned to the corresponding cobalt chloride or cobalt sulfate stripping system.

[0021] In a specific embodiment, the washing liquid from the cobalt plate washing is returned to the cobalt hydroxide leaching workshop.

[0022] In a specific embodiment, new deionized water is added to the scalding water of the cobalt plate for use as a washing liquid.

[0023] Example 2 During the cobalt plate pickling process, obtain the cobalt plate pickling status data, specifically: In the cobalt plate pickling process, the time length from the start of cleaning to the current moment is divided into several time nodes; Obtain the pickling solution concentration and pickling solution temperature corresponding to each time node in real-time state; Establish a three-dimensional model with time nodes, the pickling solution concentration and the pickling solution temperature corresponding to the time nodes, and plot the pickling solution concentration and the pickling solution temperature collected at each time node in the three-dimensional model; In the three-dimensional model, all points corresponding to the time nodes are connected with smooth curves to obtain the real-time dynamic curve of the pickling solution during the pickling process of the cobalt plate.

[0024] In the three-dimensional model, draw the standard dynamic curve of the pickling solution during the pickling process of the cobalt plate; It should be noted that the process of obtaining the standard dynamic curve of the pickling solution is as follows: In the historical process of cobalt plate pickling, the cobalt plate pickling state data corresponding to each cobalt plate pickling process (pickling solution concentration and pickling solution temperature corresponding to the time node) is obtained, the data of each cobalt plate pickling is sorted, and the pickling solution dynamic curve of each pickling process is drawn (a curve chart based on time, pickling solution temperature and pickling solution concentration); Dynamic curve of pickling liquid corresponding to each qualified pickling of cobalt plate in historical data; The dynamic curves of the pickling solution of all cobalt plates that passed the pickling test in the historical data were fitted to obtain the standard dynamic curve of the pickling solution.

[0025] In the three-dimensional model, the real-time dynamic curve of the pickling liquid is compared with the standard dynamic curve of the pickling liquid. Specifically: At each time node, the corresponding points of the pickling liquid real-time dynamic curve and the pickling liquid standard dynamic curve are connected to obtain the pickling liquid interval line between the pickling liquid real-time dynamic curve and the pickling liquid standard dynamic curve; Get the length of the pickling liquid interval line, and record it as the pickling liquid interval value; The pickling liquid interval value is compared with the pickling liquid interval threshold value; If the pickling liquid interval value is greater than or equal to the pickling liquid interval threshold, the corresponding pickling liquid interval line is recorded as the pickling liquid abnormal line; If the pickling liquid interval value is less than the pickling liquid interval threshold, the corresponding pickling liquid interval line is recorded as the pickling liquid normal line; Among them, the pickling fluid interval threshold is set by the staff based on experience.

[0026] The number of abnormal pickling liquid lines and the number of normal pickling liquid lines are obtained, and the total number of pickling liquid interval lines is obtained by summing the number of abnormal pickling liquid lines and the number of normal pickling liquid lines; The ratio of the number of pickling liquid abnormal lines to the total number of pickling liquid interval lines is calculated to obtain the pickling liquid abnormal line ratio; The pickling liquid interval values ​​corresponding to all the pickling liquid normal lines are summed and averaged to obtain the pickling liquid normal performance value; The pickling liquid interval values ​​corresponding to all pickling liquid abnormal lines are summed and averaged to obtain the pickling liquid abnormality characterization value; The difference between the normal performance value of the pickling liquid and the abnormal performance value of the pickling liquid is calculated and the absolute value is taken to obtain the performance deviation value of the pickling liquid; The pickling liquid performance deviation value is calculated by ratio with the pickling liquid interval threshold value to obtain the pickling liquid performance deviation ratio; During the pickling process of the cobalt plate, the interval time between the abnormal line ratios of adjacent pickling solutions is obtained, recorded as the line abnormality interval time, and the line abnormality interval time is calculated by ratio with the total pickling time of the cobalt plate to obtain the line abnormality interval time ratio; During the pickling process of the cobalt plate, all the abnormal interval time ratios of the lines are summed and averaged to obtain the abnormal interval value of the pickling liquid line; The pickling liquid abnormal line ratio is recorded as Sx; The pickling solution performance deviation ratio is recorded as Sc; The abnormal interval value of pickling liquid is recorded as St; That is, through the formula The pickling liquid deviation behavior value Si of the pickling liquid real-time dynamic curve relative to the pickling liquid standard dynamic curve is calculated.

[0027] The pickling liquid deviation behavior value Si is compared with the pickling liquid deviation behavior threshold Sy; If the pickling liquid deviation behavior value Si is greater than or equal to the pickling liquid deviation behavior threshold Sy, it means that the pickling state of the cobalt plate is abnormal, and a pickling abnormality signal is generated; If the pickling liquid deviation behavior value Si is less than the pickling liquid deviation behavior threshold Sy, it means that the pickling state of the cobalt plate is normal, and a normal pickling signal is generated.

[0028] Among them, the pickling liquid deviation behavior threshold is set by the staff based on experience.

[0029] Example 3 When an abnormal pickling signal is generated, it means that the pickling process of the cobalt plate is abnormal, and the cause of the abnormal state of the pickling liquid during the pickling process needs to be identified to achieve correction of the normal pickling of the cobalt plate; Abnormalities in the pickling process of cobalt plates are usually analyzed by the influence of pickling solution concentration, pickling solution temperature, or the combined influence of pickling solution concentration and pickling solution temperature; The time node corresponding to the pickling liquid abnormal line is recorded as the abnormal time node; Obtain the pickling liquid concentration value or pickling liquid temperature value corresponding to each abnormal time node; Get the data point set TNi=(Ti,Ni) of the pickling liquid concentration value at the abnormal time node under the real-time dynamic curve of the pickling liquid, where i is the number of abnormal time nodes, i=1, 2, ..., n; Ti represents the i-th abnormal time node, and Ni represents the pickling liquid concentration value corresponding to the i-th abnormal time node; Get the data point set TCi=(Ti,Ci) of the pickling liquid temperature value at the abnormal time node under the real-time dynamic curve of the pickling liquid, where i is the number of abnormal time nodes, i=1, 2, ..., n; Ti represents the i-th abnormal time node, and Ci represents the pickling liquid temperature value corresponding to the i-th abnormal time node.

[0030] Synchronously obtain the time point corresponding to the abnormal time node on the pickling liquid standard dynamic curve, and record it as the comparison time node; Obtain the pickling solution concentration value or pickling solution temperature value corresponding to the comparison time node on the pickling solution standard dynamic curve; Obtain the data point set tnj=(tj,nj) of the pickling solution concentration value at the comparison time node under the pickling solution standard dynamic curve, where i is the number of comparison time nodes, j=1, 2, ..., m; tj represents the jth comparison time node, and nj represents the pickling solution concentration value corresponding to the jth comparison time node; Obtain the data point set tcj=(tj,cj) of the pickling liquid temperature value at the comparison time node under the pickling liquid standard dynamic curve, where j is the number of comparison time nodes, j=1, 2, ..., n; tj represents the j-th comparison time node, and cj represents the pickling liquid temperature value corresponding to the j-th comparison time node.

[0031] Perform point-to-point difference calculation on the data point set TNi=(Ti,Ni)of the pickling solution concentration value at the abnormal time node and the data point set tnj=(tj,nj)of the comparison time node and the pickling solution concentration value; That is: calculate the difference between N1 in TN1=(T1,N1) and n1 in tn1=(t1,n1) and take the absolute value to obtain the abnormal concentration difference Nn1 of the pickling liquid at the first abnormal time node; Calculate the difference between N2 in TN2=(T2,N2) and n2 in tn2=(t2,n2) and take the absolute value to obtain the abnormal concentration difference Nn2 of the pickling liquid at the second abnormal time node; Calculate the difference between N3 in TN3=(T3,N3) and n3 in tn3=(t3,n3) and take the absolute value to obtain the abnormal concentration difference Nn3 of the pickling liquid at the third abnormal time node; By analogy, the abnormal concentration difference Nni of the pickling liquid at the i-th abnormal time node is obtained; Identify the abnormal concentration difference Nni of the pickling solution at each abnormal time node: If the abnormal concentration difference Nni of the pickling solution at the abnormal time node is within the preset abnormal concentration difference range of the pickling solution, the abnormal time node is recorded as a normal concentration difference node; If the abnormal concentration difference Nni of the pickling solution at the abnormal time node is outside the preset abnormal concentration difference range of the pickling solution, the abnormal time node is recorded as a concentration difference normal node.

[0032] Perform point-to-point difference calculation on the data point set TCi=(Ti,Ci) of the pickling liquid temperature value at the abnormal time node and the data point set tcj=(tj,cj) of the pickling liquid temperature value at the comparison time node; That is: calculate the difference between C1 in TCi=(Ti,Ci) and c1 in tcj=(tj,cj) and take the absolute value to obtain the abnormal temperature difference Cc1 of the pickling liquid at the first abnormal time node; Calculate the difference between C2 in TCi=(Ti,Ci) and c2 in tcj=(tj,cj) and take the absolute value to obtain the abnormal temperature difference Cc2 of the pickling liquid at the second abnormal time node; Calculate the difference between C3 in TCi=(Ti,Ci) and c3 in tcj=(tj,cj) and take the absolute value to obtain the abnormal temperature difference Cc3 of the pickling liquid at the third abnormal time node; By analogy, the abnormal temperature difference Ccj of the pickling liquid at the i-th abnormal time node is obtained; Identify the abnormal temperature difference Ccj of the pickling liquid at each abnormal time node: If the abnormal temperature difference Ccj of the pickling liquid at the abnormal time node is within the preset abnormal temperature difference range of the pickling liquid, the abnormal time node is recorded as a normal temperature difference node; If the abnormal temperature difference Ccj of the pickling liquid at the abnormal time node is outside the preset abnormal temperature difference range of the pickling liquid, the abnormal time node is recorded as a normal temperature difference node.

[0033] Obtain the number of nodes marked as normal concentration difference nodes and normal temperature difference nodes in the abnormal time nodes, and calculate the ratio of the obtained number to the number of abnormal time nodes to obtain the concentration-temperature anomaly correlation ratio; Compare and process the concentration-temperature anomaly correlation ratio with the concentration-temperature anomaly correlation ratio; If the concentration-temperature anomaly correlation ratio is greater than or equal to the concentration-temperature anomaly correlation ratio threshold, it means that the abnormal time node is disturbed by the concentration and temperature of the pickling solution, generating a concentration-temperature anomaly correlation signal; If the concentration-temperature anomaly correlation ratio is less than the concentration-temperature anomaly correlation ratio threshold, it means that the concentration and temperature of the non-acid wash solution at the abnormal time node interfere with each other, generating a concentration-temperature anomaly non-correlation signal; Based on the concentration-temperature anomaly non-correlated signal, the concentration anomaly or the temperature anomaly of the pickling solution is processed and adjusted separately to realize the correction of the pickling state during the pickling process of the cobalt plate.

[0034] Example 4 When the concentration-temperature anomaly correlation signal is generated, it means that during the pickling process of the cobalt plate, the concentration and temperature of the pickling solution interfere with the pickling state of the cobalt plate. Based on the synergistic influence of the concentration and temperature of the pickling solution, the state of the pickling solution during the pickling process of the cobalt plate is adjusted; Specific: The abnormal time nodes that are marked as both the concentration difference normal node and the temperature difference normal node are recorded as the same and different time nodes; According to the experience in the pickling process of cobalt plates, although the pickling solution concentration and the pickling solution temperature are two independent parameters, there is a certain mutual influence between them, that is, as the temperature increases, the pickling reaction rate will accelerate, so the pickling solution concentration can be appropriately reduced to achieve the same pickling effect. Conversely, if the temperature is low, the pickling solution concentration needs to be increased to ensure the pickling effect; That is, if the pickling solution temperature is high, the corresponding pickling solution concentration should be reduced; If the pickling solution temperature is low, the corresponding pickling solution concentration should be increased; Based on this; Obtain the pickling solution concentration corresponding to the maximum pickling solution temperature at the same or different time nodes, record the pickling solution temperature at the same or different time nodes as Cmax, and record the pickling solution concentration as Nci; Obtain the pickling solution concentration corresponding to the minimum pickling solution temperature at the same or different time nodes, record the pickling solution temperature at the same or different time nodes as Cmin, and record the pickling solution concentration as Nca; Calculate the difference between the pickling liquid temperature Cmax and the pickling liquid temperature Cmin and take the absolute value to obtain the pickling liquid temperature adjustment difference; The difference between the pickling solution concentration Nca and the pickling solution concentration Nci is calculated and the absolute value is taken to obtain the pickling solution concentration adjustment difference; Calculate the ratio of the pickling solution concentration adjustment difference to the pickling solution temperature adjustment difference to obtain the concentration-temperature adjustment ratio; Obtain the pickling solution concentration value and pickling solution temperature value corresponding to each time node from the start of cleaning to the current moment during the pickling process of the cobalt plate; Construct the time-pickling solution concentration curve and time-pickling solution temperature curve corresponding to the time node; Specific: The construction process of the time-pickling solution concentration curve is: With time as the X-axis and the pickling solution concentration value corresponding to each time node as the Y-axis, a first plane coordinate system is constructed; In chronological order, the time nodes and the corresponding pickling solution concentration values ​​are plotted in the first plane coordinate system, and all the points are connected in chronological order with a smooth curve to obtain a time-pickling solution concentration curve; Then, in the first plane coordinate system, a corresponding standard local curve of pickling solution concentration is selected from the standard dynamic curve of pickling solution from the start of cleaning to the current moment; The standard local curve of pickling solution concentration is constructed in the first plane coordinate system; It should be noted that the process of obtaining the standard local curve of pickling solution concentration is as follows: The pickling solution concentration value corresponding to each time node is obtained on the pickling solution standard dynamic curve, and the pickling solution concentration values ​​corresponding to the time nodes are constructed in the coordinate system in chronological order to obtain the pickling solution concentration standard local curve.

[0035] In the first plane coordinate system, the time-pickling solution concentration curve and the pickling solution concentration standard local curve are processed: The area of ​​the time-pickling solution concentration curve above the pickling solution concentration standard local curve is recorded as the high concentration area, and the areas of all high concentration areas are summed to obtain the high concentration area; The area of ​​the time-pickling solution concentration curve below the standard local curve of the pickling solution concentration is recorded as the low concentration area, and the areas of all low concentration areas are summed to obtain the low concentration area; Calculate the difference between the high-concentration area and the low-concentration area to obtain the concentration difference to be adjusted; If the concentration difference to be adjusted is greater than zero, the concentration of the pickling solution in the pickling process of the cobalt plate is reduced and the temperature of the pickling solution is increased; If the concentration difference to be adjusted is less than zero, the concentration of the pickling solution in the pickling process of the cobalt plate is increased and the temperature of the pickling solution is reduced; It should be noted that the increase or decrease of the pickling solution temperature refers to the temperature difference to be adjusted; In a specific embodiment, if the concentration difference to be adjusted is equal to zero, the concentration of the pickling solution in the pickling process of the cobalt plate is not adjusted, and the concentration of the pickling solution is adjusted according to the adjustment of the temperature of the pickling solution.

[0036] Specific: The construction process of the time-pickling solution temperature curve is: With time as the X-axis and the pickling liquid temperature value corresponding to each time node as the Y-axis, a second plane coordinate system is constructed; In chronological order, the time nodes and the corresponding pickling solution temperature values ​​are plotted in the first plane coordinate system, and all the points are connected in chronological order with a smooth curve to obtain a time-pickling solution temperature curve; Then, in the second plane coordinate system, a corresponding standard local curve of pickling solution temperature is selected from the standard dynamic curve of pickling solution from the start of cleaning to the current moment; The standard local curve of the pickling solution temperature is constructed in the first plane coordinate system; It should be noted that the process of obtaining the standard local curve of pickling liquid temperature is as follows: The pickling solution temperature value corresponding to each time node is obtained on the pickling solution standard dynamic curve, and the pickling solution temperature values ​​corresponding to the time nodes are constructed in the coordinate system in chronological order to obtain the pickling solution temperature standard local curve.

[0037] In the second plane coordinate system, the time-pickling solution temperature curve and the pickling solution temperature standard local curve are processed: The area of ​​the time-pickling solution temperature curve above the pickling solution temperature standard local curve is recorded as the high temperature area, and the areas of all high temperature areas are summed to obtain the high temperature area; The area of ​​the time-pickling solution temperature curve below the pickling solution temperature standard local curve is recorded as the low temperature area, and the areas of all low temperature areas are summed to obtain the low temperature area; Calculate the difference between the high temperature area and the low temperature area to obtain the temperature difference to be adjusted; If the temperature difference to be adjusted is greater than zero, the temperature of the pickling solution during the pickling process of the cobalt plate is reduced, and the concentration of the pickling solution is reduced; If the temperature difference to be adjusted is less than zero, the temperature of the pickling solution in the pickling process of the cobalt plate is increased, and the concentration of the pickling solution is increased; It should be noted that the increase or decrease in the concentration of the pickling solution refers to the temperature difference to be adjusted; In a specific embodiment, if the temperature difference to be adjusted is equal to zero, the temperature of the pickling solution in the pickling process of the cobalt plate is not adjusted, and the temperature of the pickling solution is adjusted according to the adjustment of the concentration of the pickling solution.

[0038] Example 5 If the concentration difference to be adjusted is greater than zero and the temperature difference to be adjusted is greater than zero, the concentration and temperature of the pickling solution are simultaneously adjusted downward; Specifically: the temperature of the pickling solution is lowered according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The adjusted concentration margin of the pickling solution and the concentration difference to be adjusted are summed to obtain the reduction in the concentration of the pickling solution, based on which the concentration of the pickling solution is adjusted.

[0039] If the concentration difference to be adjusted is greater than zero and the temperature difference to be adjusted is less than zero, the concentration of the pickling solution is adjusted downward and the temperature of the pickling solution is adjusted upward; Specifically: the temperature of the pickling solution is increased according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The difference between the adjusted concentration margin of the pickling solution and the concentration difference to be adjusted is calculated to obtain the reduction in the concentration of the pickling solution, based on which the concentration of the pickling solution is adjusted.

[0040] If the concentration difference to be adjusted is less than zero and the temperature difference to be adjusted is greater than zero, the concentration of the pickling solution is increased and the temperature of the pickling solution is decreased; Specifically: the temperature of the pickling solution is lowered according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The difference between the adjusted concentration margin of the pickling solution and the concentration difference to be adjusted is calculated to obtain the increase in the concentration of the pickling solution, based on which the concentration of the pickling solution is adjusted.

[0041] If the concentration difference to be adjusted is less than zero and the temperature difference to be adjusted is less than zero, the concentration of the pickling solution is increased and the temperature of the pickling solution is increased; Specifically: the temperature of the pickling solution is increased according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The adjusted concentration margin of the pickling solution and the concentration difference to be adjusted are summed and calculated to obtain the increase in the concentration of the pickling solution, based on which the concentration of the pickling solution is adjusted.

[0042] Thereby, online correction and adjustment of the pickling solution in the subsequent pickling process can be achieved according to the pickling solution concentration and pickling solution temperature under different conditions.

[0043] Example 6 On the basis of the above-mentioned embodiments 1-5: the electrolytic cobalt plate out of the hydrochloric acid system is prepared with a pickling solution: 10% hydrochloric acid + 5% boric acid, and the pickling time of the electrolytic cobalt plate is 40 minutes; ultrasonic water washing: the electrolytic cobalt plate is washed for 3 minutes; scalding: the scalding water temperature is 98°C, and the scalding time is 3 minutes; air drying: high-frequency fan air pressure 50Kpa, air outlet temperature 300°C, air volume 800m3 / h, from top to bottom parallel to the cobalt plate direction, air drying time 1 minute; cooling: high-frequency fan air pressure 50Kpa, air outlet temperature room temperature, air volume 800m3 / h, cooling time 5 minutes; the surface of the electrolytic cobalt plate has a bright metallic luster, and the surface does not change color after being placed in an environment of 30°C and 40% humidity for 7 days.

[0044] Example 7 On the basis of the above-mentioned Examples 1-5: hydrochloric acid system out-tank electrolytic cobalt plate, acid pickling solution: 10% hydrochloric acid, electrolytic cobalt plate acid pickling time 40min; ultrasonic water washing: electrolytic cobalt plate water washing time 3min; scalding: scalding water temperature 98℃, scalding time 3min; air drying: high-frequency fan wind pressure 50Kpa, air outlet temperature 300℃, air volume 800m3 / h, from top to bottom parallel to the cobalt plate direction, air drying time 1min; cooling: high-frequency fan wind pressure 50Kpa, air outlet temperature normal temperature, air volume 800m3 / h, cooling time 5min. The surface of the electrolytic cobalt plate has bright metallic luster, and the surface changes color in 2d under 30℃ and 40% humidity.

[0045] Example 8 On the basis of the above-mentioned Examples 1-5: the electrolytic cobalt plate of the sulfuric acid system out of the tank is equipped with pickling solution: 15% sulfuric acid + 3% boric acid, and the pickling time of the electrolytic cobalt plate is 5 minutes; ultrasonic water washing: the electrolytic cobalt plate is washed for 3 minutes; scalding: the scalding water temperature is 100°C, and the scalding time is 3 minutes; air drying: high-frequency fan wind pressure 80Kpa, air outlet temperature 200°C, air volume 900m3 / h, from top to bottom parallel to the cobalt plate direction, air drying time 2 minutes; cooling: high-frequency fan wind pressure 80Kpa, air outlet temperature normal temperature, air volume 1000m3 / h, cooling time 3 minutes. The surface of the electrolytic cobalt plate has a bright metallic luster, and the surface does not change color after being placed in an environment of 30°C and 40% humidity for 7 days.

[0046] Example 9 On the basis of the above-mentioned Examples 1-5: the electrolytic cobalt plate that was burned and blackened was prepared with pickling solution: 15% hydrochloric acid + 3% hydrogen peroxide, and the electrolytic cobalt plate was pickled for 30 minutes; ultrasonic water washing: the electrolytic cobalt plate was washed for 3 minutes; scalding: the scalding water temperature was 98°C, and the scalding time was 3 minutes; air drying: high-frequency fan air pressure 50Kpa, air outlet temperature 300°C, air volume 800m3 / h, from top to bottom parallel to the cobalt plate direction, air drying time 1min; cooling: high-frequency fan air pressure 50Kpa, air outlet temperature normal temperature, air volume 800m3 / h, cooling time 5min. The surface of the electrolytic cobalt plate has a bright metallic luster, and the surface does not change color after being placed in an environment of 30°C and 40% humidity for 7 days.

[0047] The above is a detailed description of an embodiment of the present invention, but the content is only a preferred embodiment of the present invention and cannot be considered to limit the scope of implementation of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. An electrolytic cobalt cleaning process, characterized in that: The following steps are involved: Cobalt plate pickling: Select the appropriate pickling solution according to the type of electrolytic cobalt material to be cleaned, and clean the cobalt plate in the pickling tank; During the pickling process of the cobalt plate, the pickling state data of the cobalt plate is obtained, and the pickling state of the cobalt plate is identified according to the dynamic changes of the pickling state data; When the pickling state of the cobalt plate is abnormal, the cause of the abnormal pickling state of the cobalt plate is identified, and the pickling state data of the cobalt plate is dynamically adjusted based on the abnormal cause; Cobalt plate washing: Wash the cobalt plate after pickling with water, and use ultrasonic waves in the washing tank to clean the cobalt plate; Cobalt plate scalding: scald the cobalt plate after washing, the water temperature in the scalding tank is ≥95℃, and the scalding time is 3-5min; Air drying of cobalt plate: Use hot air to air dry the washed cobalt plate from top to bottom parallel to the direction of the cobalt plate until there is no residual stain on the surface; Cobalt plate cooling: The air-dried cobalt plate is cooled by blowing cold air sideways to the cobalt plate to reduce the surface temperature of the cobalt plate to room temperature.

2. An electrolytic cobalt cleaning process according to claim 1, characterized in that: The pickling status data include pickling solution concentration and pickling solution temperature; Divide the time from the start of cleaning to the current moment into several time nodes; Obtain the pickling solution concentration and pickling solution temperature corresponding to each time node in real-time state; A three-dimensional model with time nodes, the pickling solution concentration and the pickling solution temperature corresponding to the time nodes is established, and a real-time dynamic curve of the pickling solution during the pickling process of the cobalt plate is constructed within the three-dimensional model; The real-time dynamic curve of the pickling liquid is compared with the standard dynamic curve of the pickling liquid to obtain the deviation behavior value of the real-time dynamic curve of the pickling liquid relative to the standard dynamic curve of the pickling liquid.

3. An electrolytic cobalt cleaning process according to claim 2, characterized in that: If the pickling liquid deviation behavior value is greater than or equal to the pickling liquid deviation behavior threshold, it means that the pickling state of the cobalt plate is abnormal, and a pickling abnormality signal is generated; If the pickling solution deviation behavior value is less than the pickling solution deviation behavior threshold, it means that the pickling state of the cobalt plate is normal, and a normal pickling signal is generated.

4. The electrolytic cobalt cleaning process according to claim 2, characterized in that: The process of obtaining the pickling liquid deviation behavior value is as follows: At each time node, the corresponding points of the real-time dynamic curve of the pickling liquid and the standard dynamic curve of the pickling liquid are connected to obtain the pickling liquid interval line; Get the length of the pickling liquid interval line, and record it as the pickling liquid interval value; dividing the pickling liquid interval line into a pickling liquid abnormal line and a pickling liquid normal line based on the pickling liquid interval value; The pickling liquid abnormal line ratio is obtained by processing the proportion of the number of pickling liquid abnormal lines and recorded as Sx; The pickling liquid performance deviation ratio is obtained by processing the deviation degree between the pickling liquid abnormal line and the pickling liquid normal line, and is recorded as Sc; The abnormal interval value of the pickling liquid line is obtained by processing the ratio of the interval time of the pickling liquid abnormal line, and is recorded as St; By formula The pickling liquid deviation behavior value Si of the pickling liquid real-time dynamic curve relative to the pickling liquid standard dynamic curve is calculated.

5. The electrolytic cobalt cleaning process according to claim 4, characterized in that: When an abnormal pickling signal is obtained, the time node corresponding to the abnormal pickling liquid line is recorded as the abnormal time node; Construct the data point set TNi=(Ti,Ni)of the pickling liquid concentration value and the data point set TCi=(Ti,Ci)of the pickling liquid temperature value at the abnormal time node under the real-time dynamic curve of the pickling liquid; Obtain the time point corresponding to the abnormal time node on the pickling liquid standard dynamic curve, and record it as the comparison time node; Construct the data point set tnj=(tj,nj)of the pickling solution concentration value at the comparison time node under the pickling solution standard dynamic curve and the data point set tcj=(tj,cj)of the pickling solution temperature value; The data point set TNi=(Ti,Ni)of the pickling solution concentration value at the abnormal time node and the data point set tnj=(tj,nj)of the comparison time node and the pickling solution concentration value are calculated point by point to obtain the abnormal concentration difference of the pickling solution at different abnormal time nodes; The data point set TCi=(Ti,Ci)of the pickling liquid temperature value at the abnormal time node and the data point set tcj=(tj,cj)of the pickling liquid temperature value at the comparison time node are calculated point by point to obtain the abnormal temperature difference of the pickling liquid at different abnormal time nodes.

6. The electrolytic cobalt cleaning process according to claim 5, characterized in that: When the abnormal concentration difference of the pickling solution at the abnormal time node is outside the preset abnormal concentration difference range of the pickling solution, the abnormal time node is recorded as a concentration difference normal node; When the abnormal temperature difference of the pickling liquid is outside the preset abnormal temperature difference range of the pickling liquid at the abnormal time node, the abnormal time node is recorded as a temperature difference normal node; Obtain the number of nodes marked as normal concentration difference nodes and normal temperature difference nodes in the abnormal time nodes, and calculate the ratio of the obtained number to the number of abnormal time nodes to obtain the concentration-temperature anomaly correlation ratio; The concentration-temperature anomaly correlation ratio is identified to obtain the concentration-temperature anomaly correlation signal and the concentration-temperature anomaly non-correlation signal.

7. The electrolytic cobalt cleaning process according to claim 6, characterized in that: When generating concentration-temperature anomaly correlation signals; Obtain the pickling solution concentration value and pickling solution temperature value corresponding to each time node from the start of cleaning to the current moment during the pickling process of the cobalt plate; Construct the time-pickling solution concentration curve and time-pickling solution temperature curve corresponding to the time node; In the coordinate system, the time-pickling solution concentration curve and the pickling solution concentration standard local curve are processed to obtain the concentration difference to be adjusted corresponding to the time-pickling solution concentration curve; In the coordinate system, the time-pickling solution temperature curve and the pickling solution temperature standard local curve are processed to obtain the temperature difference to be adjusted corresponding to the time-pickling solution concentration curve.

8. An electrolytic cobalt cleaning process according to claim 7, characterized in that: If the concentration difference to be adjusted is greater than zero and the temperature difference to be adjusted is greater than zero, the temperature of the pickling solution is lowered according to the temperature difference to be adjusted, and the temperature difference to be adjusted and the concentration temperature adjustment ratio are multiplied to obtain the adjusted concentration margin of the pickling solution; The adjusted concentration margin of the pickling solution and the concentration difference to be adjusted are summed to obtain the reduction in the concentration of the pickling solution; If the concentration difference to be adjusted is greater than zero and the temperature difference to be adjusted is less than zero, the temperature of the pickling solution is increased according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration-temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The difference between the adjusted concentration margin of the pickling solution and the concentration difference to be adjusted is calculated to obtain the reduction in the concentration of the pickling solution.

9. The electrolytic cobalt cleaning process according to claim 7, characterized in that: If the concentration difference to be adjusted is less than zero and the temperature difference to be adjusted is greater than zero, the temperature of the pickling solution is lowered according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration-temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The difference between the adjusted concentration margin of the pickling solution and the concentration difference to be adjusted is calculated to obtain the increase in the concentration of the pickling solution; If the concentration difference to be adjusted is less than zero and the temperature difference to be adjusted is less than zero, the temperature of the pickling solution is increased according to the temperature difference to be adjusted, and the temperature difference to be adjusted is multiplied by the concentration-temperature adjustment ratio to obtain the adjusted concentration margin of the pickling solution; The increase in the concentration of the pickling solution is calculated by summing up the adjusted concentration margin of the pickling solution and the concentration difference to be adjusted.

10. An electrolytic cobalt cleaning process according to claim 8 or 9, characterized in that: The process of obtaining the concentration temperature adjustment ratio is: The abnormal time nodes that are marked as both the concentration difference normal node and the temperature difference normal node are recorded as the same and different time nodes; The pickling solution temperature corresponding to the maximum temperature at the same or different time nodes is recorded as Cmax, and the pickling solution concentration is recorded as Nci; The pickling solution temperature corresponding to the minimum temperature in the same and different time nodes is recorded as Cmin, and the pickling solution concentration is recorded as Nca; The concentration-temperature adjustment ratio is obtained according to the temperature change and concentration change corresponding to the maximum temperature and the minimum temperature at the same and different time nodes.

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