A method and system for selective adsorption of components in a copper acid electrolyte

Abstract

This invention relates to a method and system for selective adsorption of components in a copper electrolyte. The method includes: real-time monitoring of the concentration of different target organic compounds in the copper electrolyte; comparing the real-time monitoring results with preset process standard conditions to obtain corresponding deviation values; determining the preferentially adsorbed organic compounds from among the different target organic compounds based on the deviation values; matching activated carbon with a specific oxidation degree based on the polarity of the preferentially adsorbed organic compounds; and under preset environmental conditions, adsorbing the preferentially adsorbed organic compounds using activated carbon with a specific oxidation degree, and supplementing the solution after adsorption treatment with additional additives until the additional additives reach a standard concentration. This application achieves dynamic balance control of the proportion of different target organic compounds in the copper electrolyte, thereby reducing the loss of effective additives, inhibiting the accumulation of harmful byproducts, and contributing to the improvement of copper foil quality stability.

Description

Technical Field

[0001] This invention relates to the field of electrolytic copper foil production technology, and in particular to a method and system for selective adsorption of components in an acidic copper electrolyte. Background Technology

[0002] In the production of high-end electrolytic copper foil, various organic additives (such as leveling agents, inhibitors, and brighteners) are typically added to the acid copper electrolyte (mainly composed of copper sulfate and sulfuric acid). Inhibitors are primarily strongly hydrophilic organic compounds, such as collagen, polyethers, and their derivatives, while leveling agents are mainly weakly hydrophilic or hydrophobic organic compounds, such as tetrahydrothiazolyl ketone and its derivatives, to regulate the microstructure, mechanical properties, and surface morphology of the copper foil. These additives are continuously consumed during electrodeposition, generating complex organic decomposition products. An imbalance in the additive ratio or the accumulation of byproducts will lead to fluctuations in copper foil quality, resulting in defects such as pinholes, roughness, decreased tensile strength, and reduced elongation.

[0003] Currently, the industry commonly uses the method of periodically adding activated carbon to the electrolyte and filtering it to remove impurities and some organic byproducts. However, conventional activated carbon lacks selectivity in adsorbing various organic substances. While adsorbing decomposition products, it also indiscriminately adsorbs a large amount of effective additives, leading to increased additive consumption, higher costs, and greater difficulty in accurately controlling the proportions. Therefore, there is an urgent need for a method that can selectively adsorb additives with different properties and their decomposition products, thereby achieving dynamic balance control of the organic components in the electrolyte. Summary of the Invention

[0004] Therefore, the purpose of this invention is to provide a method and system for selective adsorption of components in an acid copper electrolyte, in order to overcome the shortcomings of the prior art.

[0005] To achieve the above objectives, the present invention provides a method for the selective adsorption of components in an acid copper electrolyte, the method comprising: The concentration of different target organic compounds in the copper acid electrolyte is monitored in real time, and the real-time monitoring results are compared with preset process standard conditions to obtain the corresponding deviation value. The target organic compounds include inhibitors and leveling agents. Based on the deviation value, preferentially adsorbed organic compounds are determined from different target organic compounds, and activated carbon with a specific degree of oxidation is matched based on the polarity of the preferentially adsorbed organic compounds. Under preset environmental conditions, the preferentially adsorbed organic matter is adsorbed by activated carbon with a specific degree of oxidation, and additional additives are added to the solution after adsorption treatment until the additional additives reach a standard concentration. The additional additives are inhibitors or leveling agents consumed in the copper electrolyte after adsorption treatment.

[0006] The beneficial effects of this invention are as follows: By real-time monitoring of the concentration of different target organic compounds in the copper electrolyte, and based on the deviation between the concentration of different target organic compounds and the corresponding preset process standard conditions, the preferential adsorption organic compounds are determined. Then, activated carbon with a specific degree of oxidation is matched according to the polarity of the preferentially adsorbed organic compounds. Under preset environmental conditions, the preferentially adsorbed organic compounds are adsorbed by activated carbon with a specific degree of oxidation, thereby achieving precise removal of excess components. Then, additional additives are added until the additional additives reach the standard concentration, thereby achieving dynamic balance control of the proportion of different target organic compounds in the copper electrolyte, thereby reducing the loss of effective additives, inhibiting the accumulation of harmful by-products, and improving the stability of copper foil quality. Furthermore, the activated carbon with a specific oxidation degree is one of high oxidation degree activated carbon and low oxidation degree activated carbon, wherein the surface oxygen atom percentage of the high oxidation degree activated carbon is 10% to 15%, and the surface oxygen atom percentage of the low oxidation degree activated carbon is 3% to 5%.

[0007] Furthermore, the step of matching the polarity of the activated carbon based on the preferential adsorption of organic matter to a specific degree of oxidation includes: When the polarity of the preferentially adsorbed organic matter is hydrophilic, it is matched with activated carbon with a high degree of oxidation; When the polarity of the preferentially adsorbed organic matter is hydrophobic, it is matched with activated carbon with a low degree of oxidation.

[0008] Furthermore, the preset environmental conditions are: a preset temperature of 40℃~60℃, an addition amount of activated carbon with a specific oxidation degree of 0.1 g / L~0.3 g / L, and a contact time of 1 hour~3 hours.

[0009] Furthermore, the highly oxidized activated carbon is activated carbon obtained by treating virgin activated carbon with any one of the following methods: nitric acid oxidation, hydrogen peroxide oxidation, ozone oxidation, or air oxidation.

[0010] Furthermore, the low-oxidation activated carbon is either the original activated carbon that has not undergone deep oxidation or activated carbon obtained by deoxidizing the high-oxidation activated carbon through high-temperature inert atmosphere heat treatment.

[0011] Furthermore, the method also includes: When the polarity of the additive is hydrophilic, the additive is identified as one of collagen, polyether and its derivative compounds; When the additive is hydrophobic, it is determined that the additive is one of tetrahydrothiazothione and its derivatives.

[0012] To achieve the above objectives, the present invention also provides a system for the selective adsorption of components in an acid-copper electrolyte, used to achieve the method for the selective adsorption of components in an acid-copper electrolyte as described above, the system comprising: The real-time monitoring module is used to monitor the concentration of different target organic compounds in the copper acid electrolyte in real time, compare the real-time monitoring results with preset process standard conditions, and obtain the corresponding deviation value. The target organic compounds include inhibitors and leveling agents. A matching module is used to determine the preferred adsorption organic matter from different target organic matter based on the deviation value, and to match activated carbon with a specific degree of oxidation based on the polarity of the preferred adsorption organic matter. An adsorption module is used to adsorb the preferentially adsorbed organic matter using activated carbon with a specific degree of oxidation under preset environmental conditions, and to replenish the solution after adsorption treatment with additional additives until the additional additives reach a standard concentration. The additional additives are inhibitors or leveling agents consumed in the copper electrolyte after adsorption treatment. Attached Figure Description

[0013] Figure 1 This is a flowchart of a method for selective adsorption of components in a copper electrolyte according to an embodiment of the present invention; Figure 2 This is a comparison chart of the adsorption capacity of activated carbon with different oxidation levels for collagen and tetrahydrothiazolyl thiophene according to an embodiment of the present invention.

[0014] The following detailed description, in conjunction with the accompanying drawings, will further illustrate the present invention. Detailed Implementation

[0015] To make the objectives, technical solutions, and advantages of this application clearer, the application is described and illustrated below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application. All other embodiments obtained by those skilled in the art based on the embodiments provided in this application without inventive effort are within the scope of protection of this application.

[0016] Obviously, the accompanying drawings described below are merely some examples or embodiments of this application. Those skilled in the art can apply this application to other similar scenarios based on these drawings without any inventive effort. Furthermore, it is understood that although the efforts made in this development process may be complex and lengthy, for those skilled in the art related to the content disclosed in this application, any changes to design, manufacturing, or production based on the technical content disclosed in this application are merely conventional technical means and should not be construed as insufficient disclosure of the content of this application.

[0017] In this application, the reference to "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment that is mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this application may be combined with other embodiments without conflict.

[0018] Unless otherwise defined, the technical or scientific terms used in this application shall have the ordinary meaning understood by one of ordinary skill in the art to which this application pertains. The terms “a,” “an,” “an,” “the,” and similar words used in this application do not indicate quantity limitation and may indicate singular or plural. The terms “comprising,” “including,” “having,” and any variations thereof used in this application are intended to cover non-exclusive inclusion; for example, a process, method, system, product, or device that includes a series of steps or modules (units) is not limited to the listed steps or units, but may also include steps or units not listed, or may include other steps or units inherent to these processes, methods, products, or devices. The terms “connected,” “linked,” “coupled,” and similar words used in this application are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. “Multiple” used in this application refers to two or more. “And / or” describes the relationship between related objects, indicating that three relationships may exist; for example, “A and / or B” can represent: A alone, A and B simultaneously, and B alone. The character " / " generally indicates that the preceding and following objects are in an "or" relationship. The terms "first," "second," and "third" used in this application are merely to distinguish similar objects and do not represent a specific ordering of the objects.

[0019] Example 1 Please see Figure 1 The flowchart below shows the method for selective adsorption of components in an acid copper electrolyte according to the first embodiment of the present invention. The method includes the following steps: Step S101: Monitor the concentration of different target organic compounds in the copper acid electrolyte in real time, compare the real-time monitoring results with the preset process standard conditions, and obtain the corresponding deviation value. The target organic compounds include inhibitors and leveling agents. The electrochemical concentrations of inhibitors and leveling agents in the copper electrolyte were tested using cyclic voltammetry (CVS). The real-time monitoring results were compared with preset process standard conditions to obtain the corresponding deviation values. The inhibitors were hydrophilic organic compounds, including strongly hydrophilic collagen, polyethers, and mixtures of their decomposition products. The leveling agents were hydrophobic organic compounds, including weakly hydrophilic and hydrophobic tetrahydrothiazolidinone and mixtures of its decomposition products.

[0020] Step S102: Based on the deviation value, determine the preferred adsorption organic matter from different target organic matter, and match activated carbon with a specific degree of oxidation based on the polarity of the preferred adsorption organic matter; In this process, based on the deviation between the monitoring results and the preset process standards, it is determined whether hydrophilic or hydrophobic organic matter needs to be preferentially adsorbed. The preferentially adsorbed organic matter is an excess of inhibitors or leveling agents.

[0021] Furthermore, the step of matching the polarity of the activated carbon based on the preferential adsorption of organic matter to a specific degree of oxidation includes: When the polarity of the preferentially adsorbed organic matter is hydrophilic, it is matched with activated carbon with a high degree of oxidation; When the polarity of the preferentially adsorbed organic matter is hydrophobic, it is matched with activated carbon with a low degree of oxidation.

[0022] It should be noted that the activated carbon with a specific oxidation degree is one of high-oxidation-degree activated carbon and low-oxidation-degree activated carbon. The high-oxidation-degree activated carbon has a surface oxygen atom percentage of 10% to 15%. This high-oxidation-degree activated carbon has abundant oxygen-containing functional groups (such as carboxyl groups, hydroxyl groups, and lactone groups) on its surface, resulting in high oxygen content and strong hydrophilicity. It has a stronger adsorption affinity for highly polar hydrophilic organic compounds. The low-oxidation-degree activated carbon has a surface oxygen atom percentage of 3% to 5%. This low-oxidation-degree activated carbon has fewer oxygen-containing functional groups and lower oxygen content on its surface, resulting in strong hydrophobicity and a stronger adsorption affinity for non-polar or weakly polar organic compounds.

[0023] Step S103: Under preset environmental conditions, the preferentially adsorbed organic matter is adsorbed by activated carbon with a specific degree of oxidation, and additional additives are added to the solution after adsorption treatment until the additional additives reach the standard concentration. The additional additives are inhibitors or leveling agents consumed in the copper electrolyte after adsorption treatment.

[0024] Furthermore, the preset environmental conditions are: a preset temperature of 40℃~60℃, an addition amount of activated carbon with a specific oxidation degree of 0.1 g / L~0.3 g / L, and a contact time of 1 hour~3 hours.

[0025] It should be noted that the adsorption treatment under the preset environmental conditions specifically involves adding activated carbon with a specific oxidation level of 0.1 g / L to 0.3 g / L to the electrolyte circulation system or auxiliary treatment tank, and performing stirred contact adsorption at 40℃ to 60℃ for 1 to 3 hours. After adsorption is complete, the activated carbon with the specific oxidation level is completely removed by precision filtration. Then, the electrochemical concentrations of inhibitors and leveling agents in the solution before and after adsorption treatment are detected. Based on the detection results of organic matter in the copper acid electrolyte after adsorption treatment, the consumed additives are replenished until the process standard concentration is reached, so that the additives in the copper acid electrolyte are restored and maintained within the optimal range.

[0026] Through the above steps, by real-time monitoring of the concentration of different target organic compounds in the copper acid electrolyte, and based on the deviation between the concentration of different target organic compounds and the corresponding preset process standard conditions, the preferential adsorption organic compounds are determined. Then, activated carbon with a specific degree of oxidation is matched according to the polarity of the preferentially adsorbed organic compounds. Under preset environmental conditions, the preferentially adsorbed organic compounds are adsorbed by activated carbon with a specific degree of oxidation to achieve precise removal of excess components. Then, additional additives are added until the additional additives reach the standard concentration, thereby achieving dynamic balance control of the proportion of different target organic compounds in the copper acid electrolyte.

[0027] The effective effects are as follows: High selectivity and precise control: Overcoming the limitations of indiscriminate adsorption by traditional activated carbon, it achieves selective adsorption of both hydrophilic and hydrophobic organic compounds. This allows operators to remove target impurities or excess components like "precision guidance," thereby actively and precisely controlling the proportions of various additives in the electrolyte to maintain their optimal synergistic effect. Reduce the loss of effective additives and lower costs: Due to the selective adsorption, when removing harmful decomposition products or excess additives, the adsorption of other types of additives at the required concentration is significantly reduced, thereby greatly reducing the unnecessary consumption of effective additives and saving production costs. Inhibiting the accumulation of by-products and improving quality stability: It is beneficial to target and remove specific decomposition products that are difficult to treat by conventional methods, prevent them from accumulating in the electrolyte, reduce the factors that cause copper foil defects from the root, and improve the quality consistency and stability of copper foil products. It has strong process adaptability and flexible operation: depending on the specific situation of different inhibitor and leveling agent formulations and the fluctuation of the electrochemical concentration of inhibitor and leveling agent in the electrolyte at different production stages, activated carbon with different oxidation degrees or their combination can be flexibly selected. It has strong process adaptability and is easy to integrate into the existing production process.

[0028] Furthermore, the percentage of oxidation atoms on the surface of the highly oxidized activated carbon is preferably 10% to 15%.

[0029] Furthermore, the percentage of oxidation atoms on the surface of the low-oxidation activated carbon is preferably 3% to 5%.

[0030] Furthermore, the highly oxidized activated carbon is activated carbon obtained by treating virgin activated carbon with any one of the following methods: nitric acid oxidation, hydrogen peroxide oxidation, ozone oxidation, or air oxidation.

[0031] The preparation method of the highly oxidized activated carbon includes, but is not limited to: oxidizing conventional activated carbon under heating conditions using concentrated nitric acid, hydrogen peroxide, ozone, or oxygen from the air.

[0032] Furthermore, the low-oxidation activated carbon is either the original activated carbon that has not undergone deep oxidation or activated carbon obtained by deoxidizing the high-oxidation activated carbon through high-temperature inert atmosphere heat treatment.

[0033] The low-oxidation activated carbon can be commercially available, untreated activated carbon, or it can be obtained by removing oxygen-containing functional groups from high-oxidation activated carbon under an inert atmosphere through high-temperature heat treatment.

[0034] Furthermore, the method also includes: When the polarity of the additive is hydrophilic, the additive is identified as one of collagen, polyether and its derivative compounds; When the additive is hydrophobic, it is determined that the additive is one of tetrahydrothiazothione and its derivatives.

[0035] Example 2 The method for selective adsorption of components in the copper electrolyte of the second embodiment of the present invention, specifically for controlling the excess of hydrophobic organic matter, is implemented as follows under the first preset environmental conditions: In an electrolytic copper foil production line, the concentration of hydrophobic leveling agent (tetrahydrothiazolyl thiophene) in the electrolyte was excessive, while the electrochemical concentration of the inhibitor was normal, resulting in a significantly higher tensile strength of the copper foil. At this point, low-oxidation activated carbon (EDX measurement showed a surface oxygen atom content of 4.8%) was selected and added to the electrolyte auxiliary treatment tank at a dosage of 0.1 g / L. After stirring and adsorption at 50°C for 3 hours, the mixture was precisely filtered. Testing revealed that the leveling agent concentration decreased by 18.3%, and the inhibitor concentration decreased by 3.6%. The consumable additives were then replenished according to the process ratio, quickly restoring the ratio to the optimal process window, and the tensile strength and elongation of the copper foil returned to normal.

[0036] Example 3 The method for selective adsorption of components in the copper electrolyte of the present invention in the third embodiment of the present invention, specifically for controlling the excess of hydrophobic organic matter, is implemented as follows under the second preset environmental conditions: In an electrolytic copper foil production line, the concentration of hydrophobic leveling agent (tetrahydrothiazolyl thiophene) in the electrolyte was excessive, while the electrochemical concentration of the inhibitor was normal, resulting in significantly higher tensile strength of the copper foil. At this point, low-oxidation activated carbon (EDX measurement showed a surface oxygen atom content of 4.8%) was selected and added to the electrolyte auxiliary treatment tank at a dosage of 0.1 g / L. After stirring and adsorption at 50°C for 4 hours, the mixture was precisely filtered. Testing revealed that the leveling agent concentration decreased by 18.5%, and the inhibitor concentration decreased by 3.7%. The consumable additives were then replenished according to the process ratio, quickly restoring the ratio to the optimal process window, and the tensile strength and elongation of the copper foil returned to normal.

[0037] Example 4 The method for selective adsorption of components in the copper electrolyte of the fourth embodiment of the present invention, specifically for controlling the excess of hydrophobic organic matter, is implemented under the third preset environmental condition as follows: In an electrolytic copper foil production line, the concentration of hydrophobic leveling agent (tetrahydrothiazolyl thiophene) in the electrolyte was excessive, while the electrochemical concentration of the inhibitor was normal, resulting in a significantly higher tensile strength of the copper foil. At this point, low-oxidation activated carbon (EDX measurement showed a surface oxygen atom content of 4.8%) was selected and added to the electrolyte auxiliary treatment tank at a dosage of 0.2 g / L. After stirring and adsorption at 50°C for 3 hours, the mixture was precisely filtered. Testing revealed that the leveling agent concentration decreased by 31.0%, and the inhibitor concentration decreased by 6.8%. The consumable additives were then replenished according to the process ratio, quickly restoring the ratio to the optimal process window, and the tensile strength of the copper foil returned to normal.

[0038] Example 5 The method for selective adsorption of components in the copper electrolyte of the fifth embodiment of the present invention, specifically for controlling the excess of hydrophobic organic matter, is implemented under the fourth preset environmental condition as follows: In an electrolytic copper foil production line, the concentration of hydrophobic leveling agent (tetrahydrothiazolyl thiophene) in the electrolyte was excessive, while the electrochemical concentration of the inhibitor was normal, resulting in a significantly higher tensile strength of the copper foil. At this point, low-oxidation activated carbon (EDX measurement showed a surface oxygen atom content of 4.8%) was selected and added to the electrolyte auxiliary treatment tank at a dosage of 0.3 g / L. After stirring and adsorption at 50°C for 3 hours, the mixture was precisely filtered. Testing revealed that the leveling agent concentration decreased by 41.6%, and the inhibitor concentration decreased by 9.7%. The consumable additives were then replenished according to the process ratio, quickly restoring the ratio to the optimal process window, and the tensile strength of the copper foil returned to normal.

[0039] Example 6 The method for selective adsorption of acid copper electrolyte components in the sixth embodiment of the present invention, specifically for controlling the excess of hydrophobic organic matter, is implemented under the fifth preset environmental conditions as follows: In an electrolytic copper foil production line, the concentration of hydrophobic leveling agent (tetrahydrothiazolyl thiophene) in the electrolyte was excessive, while the electrochemical concentration of the inhibitor was normal, resulting in significantly higher tensile strength of the copper foil. At this point, low-oxidation activated carbon (EDX measurement showed a surface oxygen atom content of 4.8%) was selected and added to the electrolyte auxiliary treatment tank at a dosage of 0.02 g / L. After stirring and adsorption at 50°C for 3 hours, the mixture was precisely filtered. Testing revealed that the leveling agent concentration decreased by 4.8%, and the inhibitor concentration decreased by 1.5%. Even after replenishing the consumable additives according to the process ratio, the leveling agent concentration still exceeded the standard range, and the tensile strength of the copper foil exceeded the standard.

[0040] Example 7 The method for selective adsorption of acid copper electrolyte components in the seventh embodiment of the present invention, specifically for controlling the excess of hydrophobic organic matter, is implemented under the sixth preset environmental conditions as follows: In an electrolytic copper foil production line, the concentration of hydrophobic leveling agent (tetrahydrothiazolyl thiophene) in the electrolyte was excessive, while the electrochemical concentration of the inhibitor was normal, resulting in a significantly higher tensile strength of the copper foil. At this point, low-oxidation activated carbon (EDX measurement showed a surface oxygen atom content of 4.8%) was selected and added to the electrolyte auxiliary treatment tank at a dosage of 0.4 g / L. After stirring and adsorption at 50°C for 3 hours, the mixture was precisely filtered. Testing revealed that the leveling agent concentration decreased by 48.6%, and the inhibitor concentration decreased by 14.6%. When the additives were replenished according to the process ratio for normal production, the tensile strength of the copper foil remained low.

[0041] Example 8 The method for selective adsorption of acid copper electrolyte components in the eighth embodiment of the present invention, specifically for controlling the excess of hydrophilic organic matter, is implemented under the seventh preset environmental condition as follows: In an electrolytic copper foil production line, excessive addition of highly hydrophilic inhibitors or accumulation of decomposition products led to inhibitor electrochemical concentrations exceeding standards, resulting in a decrease in the tensile strength of the copper foil. Analysis confirmed that the leveling agent concentration was normal. At this point, highly oxidized activated carbon (EDX measured surface oxygen content of 10.9%) treated with concentrated nitric acid reflux oxidation was selected. It was added to the electrolyte auxiliary treatment tank at a dosage of 0.1 g / L, and after stirring and adsorption at 50°C for 3 hours, it was precisely filtered. After adsorption, the inhibitor concentration in the electrolyte decreased according to CVS tests, while the leveling agent concentration remained essentially unchanged. The tensile strength of the copper foil after treatment was significantly improved, increasing by 9.8%.

[0042] Example 9 The method for selective adsorption of acid copper electrolyte components in the ninth embodiment of the present invention, specifically for controlling the excess of hydrophilic organic matter, is implemented under the eighth preset environmental condition as follows: In the electrolytic copper foil production line, excessive addition of strongly hydrophilic inhibitors or accumulation of decomposition products led to the inhibitor electrochemical concentration exceeding the standard, resulting in a decrease in the tensile strength of the copper foil. Analysis confirmed that the leveling agent concentration was normal. At this point, highly oxidized activated carbon (EDX measured surface oxygen atom content of 10.9%) treated with concentrated nitric acid reflux oxidation was selected. It was added to the electrolyte auxiliary treatment tank at a dosage of 0.2 g / L, and after stirring and adsorption at 50°C for 3 hours, it was precisely filtered. After adsorption, the inhibitor concentration in the electrolyte decreased according to CVS tests, while the leveling agent concentration remained essentially unchanged. The tensile strength of the copper foil was significantly improved after treatment, increasing by 11.1%.

[0043] Example 10 The method for selective adsorption of acid copper electrolyte components in the tenth embodiment of the present invention, specifically for controlling the excess of hydrophilic organic matter, is implemented under the ninth preset environmental condition as follows: In an electrolytic copper foil production line, excessive addition of highly hydrophilic inhibitors or accumulation of decomposition products led to inhibitor electrochemical concentrations exceeding standards, resulting in a decrease in the tensile strength of the copper foil. Analysis confirmed that the leveling agent concentration was normal. At this point, highly oxidized activated carbon (EDX measured surface oxygen content of 10.9%) treated with concentrated nitric acid reflux oxidation was selected. It was added to the electrolyte auxiliary treatment tank at a dosage of 0.3 g / L, and after stirring and adsorption at 50°C for 3 hours, it was precisely filtered. After adsorption, the inhibitor concentration in the electrolyte decreased according to CVS tests, while the leveling agent concentration remained essentially unchanged. The tensile strength of the copper foil after treatment was significantly improved, increasing by 12.4%.

[0044] Example 11 The method for selective adsorption of acid copper electrolyte components in the eleventh embodiment of the present invention, specifically for controlling the excess of hydrophilic organic matter, is implemented under the tenth preset environmental condition as follows: In an electrolytic copper foil production line, excessive addition of highly hydrophilic inhibitors or accumulation of decomposition products led to inhibitor electrochemical concentrations exceeding standards, resulting in a decrease in the tensile strength of the copper foil. Analysis confirmed that the leveling agent concentration was normal. At this point, highly oxidized activated carbon (EDX measured surface oxygen content of 10.9%) treated with concentrated nitric acid reflux oxidation was selected. It was added to the electrolyte auxiliary treatment tank at a dosage of 0.3 g / L, and after stirring and adsorption at 50°C for 2 hours, it was precisely filtered. After adsorption, the inhibitor concentration in the electrolyte decreased according to CVS tests, while the leveling agent concentration remained essentially unchanged. The tensile strength of the copper foil was significantly improved after treatment, increasing by 11.7%.

[0045] Example 12 The method for selective adsorption of components in the acid copper electrolyte in the twelfth embodiment of the present invention, specifically for controlling the excess of hydrophilic organic matter, is implemented under the eleventh preset environmental condition as follows: In the electrolytic copper foil production line, excessive addition of strong hydrophilic inhibitors or accumulation of decomposition products led to the inhibitor electrochemical concentration exceeding the standard, resulting in a decrease in the tensile strength of the copper foil. Analysis confirmed that the leveling agent concentration was normal. At this point, highly oxidized activated carbon (EDX measured surface oxygen atom content of 10.9%) treated with concentrated nitric acid reflux oxidation was selected. It was added to the electrolyte auxiliary treatment tank at a dosage of 0.02 g / L, and after stirring and adsorption at 50°C for 2 hours, it was precisely filtered. After adsorption, the inhibitor concentration in the electrolyte decreased slightly according to CVS tests, while the leveling agent concentration remained essentially unchanged. The tensile strength of the copper foil was not effectively improved after treatment, increasing by only 2.3%.

[0046] Example 13 The method for selective adsorption of components in the acid copper electrolyte in the thirteenth embodiment of the present invention, specifically for controlling the excess of hydrophilic organic matter, is implemented under the twelfth preset environmental condition as follows: In the electrolytic copper foil production line, excessive addition of strongly hydrophilic inhibitors or accumulation of decomposition products led to inhibitor electrochemical concentrations exceeding standards, resulting in a decrease in the tensile strength of the copper foil. Analysis confirmed that the leveling agent concentration was normal. At this point, highly oxidized activated carbon (EDX measured surface oxygen atom content of 10.9%) treated with concentrated nitric acid reflux oxidation was selected. It was added to the electrolyte auxiliary treatment tank at a dosage of 0.4 g / L, and after stirring and adsorption at 50°C for 2 hours, it was precisely filtered. After adsorption, the inhibitor concentration in the electrolyte decreased significantly according to CVS tests, and the leveling agent concentration decreased simultaneously. The tensile strength of the copper foil was not effectively improved after treatment, increasing by only 4.5%.

[0047] Example 14 The method for selective adsorption of components in the acid copper electrolyte in the fourteenth embodiment of the present invention, specifically for controlling the excess of hydrophobic organic matter, employs activated carbon with a lower oxidation degree (2.1% surface oxygen atom content) to adsorb the electrolyte in Example 2. The specific implementation is as follows: In an electrolytic copper foil production line, the concentration of hydrophobic leveling agent (tetrahydrothiazolyl thiophene) in the electrolyte was excessive, while the electrochemical concentration of the inhibitor was normal, resulting in a significantly higher tensile strength of the copper foil. At this point, low-oxidation activated carbon (EDX measurement showed a surface oxygen atom content of 2.1%) was selected and added to the electrolyte auxiliary treatment tank at a dosage of 0.1 g / L. The mixture was stirred and adsorbed at 50°C for 3 hours. Testing revealed that due to the poor hydrophilicity of the activated carbon, it agglomerated significantly in the acidic electrolyte, exhibiting poor dispersibility and failing to perform its adsorption function. Further testing showed that the leveling agent concentration decreased by 7%, and the wetting agent concentration decreased by 1%.

[0048] Example 15 The method for selective adsorption of components in the acid copper electrolyte in the fifteenth embodiment of the present invention, specifically for controlling the excess of hydrophilic organic matter, employs activated carbon with a higher degree of oxidation (18.6% surface oxygen atom content) to adsorb the electrolyte from Example 8. The specific implementation is as follows: In the electrolytic copper foil production line, excessive addition of strongly hydrophilic inhibitors or accumulation of decomposition products led to an excess of the inhibitor's electrochemical concentration beyond the standard, resulting in a decrease in the tensile strength of the copper foil. Analysis confirmed that the leveling agent concentration was normal. At this point, highly oxidized activated carbon (EDX measurement showed a surface oxygen atom content of 18.6%), treated with concentrated nitric acid reflux oxidation, was selected. It was added to the electrolyte auxiliary treatment tank at a dosage of 0.1 g / L, stirred and adsorbed at 50°C for 3 hours, and then precisely filtered. Excessive adsorption of strongly hydrophilic organic matter in the electrolyte caused a 23% decrease in the inhibitor concentration, resulting in copper foil warping that failed the test, and tensile strength significantly exceeding the process range.

[0049] Example 16 The method for selective adsorption of components in the acid copper electrolyte in the sixteenth embodiment of the present invention, specifically for controlling the excess of hydrophobic organic matter, involves using ordinary activated carbon with a surface oxygen atom content of approximately 7% to adsorb the electrolyte in Example 2. The specific implementation is as follows: In an electrolytic copper foil production line, the concentration of hydrophobic leveling agent (tetrahydrothiazolyl thiophene) in the electrolyte was excessive, while the electrochemical concentration of the inhibitor was normal, resulting in significantly higher tensile strength of the copper foil. At this point, low-oxidation activated carbon (EDX measurement showed a surface oxygen atom content of 7%) was selected and added to the electrolyte auxiliary treatment tank at a dosage of 0.1 g / L. After stirring and adsorption at 50°C for 3 hours, the mixture was precisely filtered. Testing revealed that the leveling agent concentration decreased by 12%, and the inhibitor concentration decreased by 8% simultaneously. Replenishing the consumable additives according to the process ratio did not effectively correct the ratio, the copper foil quality problem persisted, and both additives were unnecessarily wasted.

[0050] In summary, the specific examples in Examples 2-16 above fully demonstrate the effectiveness and superiority of the selective adsorption method for acid copper electrolysis components described in Example 1. This method achieves selective adsorption by controlling the degree of activated carbon oxidation, thereby precisely controlling the proportions of additives with different properties. Figure 2 The figure shows a comparison of the adsorption capacity of activated carbon with different oxidation levels for collagen and tetrahydrothiazolidinone.

[0051] Example 17 The system for selective adsorption of components in an acid copper electrolyte according to the seventeenth embodiment of the present invention, the system comprising: The real-time monitoring module is used to monitor the concentration of different target organic compounds in the copper acid electrolyte in real time, compare the real-time monitoring results with preset process standard conditions, and obtain the corresponding deviation value. The target organic compounds include inhibitors and leveling agents. A matching module is used to determine the preferred adsorption organic matter from different target organic matter based on the deviation value, and to match activated carbon with a specific degree of oxidation based on the polarity of the preferred adsorption organic matter. An adsorption module is used to adsorb the preferentially adsorbed organic matter using activated carbon with a specific degree of oxidation under preset environmental conditions, and to replenish the solution after adsorption treatment with additional additives until the additional additives reach a standard concentration. The additional additives are inhibitors or leveling agents consumed in the copper electrolyte after adsorption treatment.

[0052] In practice, the concentrations of different target organic compounds in the copper electrolyte are monitored in real time. Based on the deviations between the concentrations of different target organic compounds and the corresponding preset process standard conditions, the organic compounds to be preferentially adsorbed are determined. Then, activated carbon with a specific degree of oxidation is matched according to the polarity of the preferentially adsorbed organic compounds. Under preset environmental conditions, the preferentially adsorbed organic compounds are adsorbed by activated carbon with a specific degree of oxidation, thereby achieving precise removal of excess components. Additional additives are then added until the additional additives reach the standard concentration. This achieves dynamic balance control of the proportions of different target organic compounds in the copper electrolyte, thereby reducing the loss of effective additives, inhibiting the accumulation of harmful byproducts, and improving the stability of copper foil quality.

[0053] Furthermore, the activated carbon with a specific oxidation degree is one of high oxidation degree activated carbon and low oxidation degree activated carbon, wherein the surface oxygen atom percentage of the high oxidation degree activated carbon is 10% to 15%, and the surface oxygen atom percentage of the low oxidation degree activated carbon is 3% to 5%.

[0054] Furthermore, the matching module includes: The first matching unit is used to match highly oxidized activated carbon when the polarity of the preferentially adsorbed organic matter is hydrophilic. The second matching unit is used to match activated carbon with a low degree of oxidation when the polarity of the preferentially adsorbed organic matter is hydrophobic.

[0055] Furthermore, the preset environmental conditions are: a preset temperature of 40℃~60℃, an addition amount of activated carbon with a specific oxidation degree of 0.1 g / L~0.3 g / L, and a contact time of 1 hour~3 hours.

[0056] Furthermore, the highly oxidized activated carbon is activated carbon obtained by treating virgin activated carbon with any one of the following methods: nitric acid oxidation, hydrogen peroxide oxidation, ozone oxidation, or air oxidation.

[0057] Furthermore, the low-oxidation activated carbon is either the original activated carbon that has not undergone deep oxidation or activated carbon obtained by deoxidizing the high-oxidation activated carbon through high-temperature inert atmosphere heat treatment.

[0058] Furthermore, the system also includes: The first determining module is used to determine that the additive is one of collagen, polyether and its derivative compounds when the polarity of the additive is hydrophilic. The second determining module is used to determine that the additive is one of tetrahydrothiazolium thione and its derivatives when the polarity of the additive is hydrophobic.

[0059] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0060] Without causing conflict, those skilled in the art can freely combine and use the above-mentioned additional technical features.

[0061] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for selective adsorption of components in an acid copper electrolyte, characterized in that, The method includes: The concentration of different target organic compounds in the copper acid electrolyte is monitored in real time, and the real-time monitoring results are compared with preset process standard conditions to obtain the corresponding deviation value. The target organic compounds include inhibitors and leveling agents. Based on the deviation value, preferentially adsorbed organic compounds are determined from different target organic compounds, and activated carbon with a specific degree of oxidation is matched based on the polarity of the preferentially adsorbed organic compounds. Under preset environmental conditions, the preferentially adsorbed organic matter is adsorbed by activated carbon with a specific degree of oxidation, and additional additives are added to the solution after adsorption treatment until the additional additives reach a standard concentration. The additional additives are inhibitors or leveling agents consumed in the copper electrolyte after adsorption treatment.

2. The method for selective adsorption of components in an acid copper electrolyte according to claim 1, characterized in that, The activated carbon with a specific oxidation degree is one of high oxidation degree activated carbon and low oxidation degree activated carbon. The surface oxygen atom percentage of the high oxidation degree activated carbon is 10% to 15%, and the surface oxygen atom percentage of the low oxidation degree activated carbon is 3% to 5%.

3. The method for selective adsorption of components in an acid copper electrolyte according to claim 2, characterized in that, The step of matching the polarity of activated carbon with a specific degree of oxidation based on the preferential adsorption of organic matter includes: When the polarity of the preferentially adsorbed organic matter is hydrophilic, it is matched with activated carbon with a high degree of oxidation; When the polarity of the preferentially adsorbed organic matter is hydrophobic, it is matched with activated carbon with a low degree of oxidation.

4. The method for selective adsorption of components in an acid copper electrolyte according to claim 1, characterized in that, The preset environmental conditions are: preset temperature of 40℃~60℃, addition amount of activated carbon with specific oxidation degree of 0.1 g / L~0.3 g / L, and contact time of 1 hour~3 hours.

5. The method for selective adsorption of components in an acid copper electrolyte according to claim 2, characterized in that, The highly oxidized activated carbon is activated carbon obtained by treating raw activated carbon with any one of the following methods: nitric acid oxidation, hydrogen peroxide oxidation, ozone oxidation, or air oxidation.

6. The method for selective adsorption of components in an acid copper electrolyte according to claim 2, characterized in that, The low-oxidation activated carbon is either the original activated carbon that has not undergone deep oxidation or activated carbon obtained by deoxidizing the high-oxidation activated carbon through high-temperature inert atmosphere heat treatment.

7. The method for selective adsorption of components in an acid copper electrolyte according to claim 1, characterized in that, The method further includes: When the polarity of the additive is hydrophilic, the additive is identified as one of collagen, polyether and its derivative compounds; When the additive is hydrophobic, it is determined that the additive is one of tetrahydrothiazothione and its derivatives.

8. A system for selective adsorption of components in an acid-copper electrolyte, used to achieve the method for selective adsorption of components in an acid-copper electrolyte as described in any one of claims 1-7, characterized in that, The system includes: The real-time monitoring module is used to monitor the concentration of different target organic compounds in the copper acid electrolyte in real time, compare the real-time monitoring results with preset process standard conditions, and obtain the corresponding deviation value. The target organic compounds include inhibitors and leveling agents. A matching module is used to determine the preferred adsorption organic matter from different target organic matter based on the deviation value, and to match activated carbon with a specific degree of oxidation based on the polarity of the preferred adsorption organic matter. An adsorption module is used to adsorb the preferentially adsorbed organic matter using activated carbon with a specific degree of oxidation under preset environmental conditions, and to replenish the solution after adsorption treatment with additional additives until the additional additives reach a standard concentration. The additional additives are inhibitors or leveling agents consumed in the copper electrolyte after adsorption treatment.

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