An arsenic-antimony-bismuth purifying agent, a preparation method, application and recovery method thereof

Abstract

The present application belongs to the field of solution purifying agent, and particularly relates to an arsenic-antimony-bismuth purifying agent, a preparation method, application and recovery method thereof. The preparation method comprises the following steps: mixing an antimony-containing compound with triethanolamine alcohol, stirring uniformly, adding an oxidizing agent to perform oxidation treatment, and drying to obtain the arsenic-antimony-bismuth purifying agent. The present application can efficiently prepare a transition state special crystal form Sb(III) and Sb(V) compound as the arsenic-antimony-bismuth purifying agent, which is used for efficient purification treatment of copper electrolyte and can make the copper electrolyte form a stable self-purification effect. Meanwhile, the generated precipitate slag after use can be further recovered and prepared into the arsenic-antimony-bismuth purifying agent, which has extremely high economic value and environmental protection value.

Description

Technical Field

[0001] This invention belongs to the field of solution purification agents, and particularly relates to an arsenic-antimony-bismuth purification agent, its preparation method, application and recycling method. Background Technology

[0002] Arsenic, antimony, and bismuth are common associated elements in copper minerals. During the electrolytic refining of copper, impurity elements in crude copper dissolve in the electrolyte through an electrochemical process and gradually accumulate. Because the potentials of these impurity elements are similar to those of copper, when these impurity elements accumulate to a certain level in the electrolyte, they will be deposited simultaneously with copper at the cathode during the electrolytic refining process, greatly affecting the quality of the cathode copper.

[0003] Currently, the most widely used method in the purification and impurity removal of copper electrolyte is the electrowinning process. This process is widely used, has good impurity removal effect, and has a good industrial foundation. However, this method has the following disadvantages: 1) Using lead plates as anodes results in extremely high electrolytic cell voltage and high energy consumption; 2) The process easily generates highly toxic arsine gas, threatening worker safety; 3) Black copper contains about 60% copper, which is difficult to utilize, resulting in copper loss.

[0004] On September 15, 2017, the Chinese Patent Office disclosed a copper electrolyte purification process, application publication number CN110983376A. This process mainly improves upon the traditional electrodeposition method by using sulfur dioxide to reduce the copper electrolyte before sulfide precipitation, thereby reducing hydrogen sulfide consumption, lowering costs, and improving the purification efficiency of the copper electrolyte. However, this process is relatively complex and fails to solve the problems of easily generating highly toxic gases and high copper loss inherent in the electrodeposition method.

[0005] Meanwhile, the article "Exploration of new indirect self-purification process for copper electrolyte[J]. Metallurgical smelting, 2021, 03: 8-10" by Wenzhong Tang points out the use of high-valence antimony oxides for self-purification of copper electrolytes. This involves Sb(V) reacting with Me(III) in the electrolyte to form antimonates with very low solubility, thereby removing the main impurities in the solution. However, this purifier requires a settling time of over 4 hours, and during the regeneration process, the impurity metal Bi continuously accumulates in the regenerating purifier, thus reducing its self-purification effect.

[0006] Therefore, it is very important to develop a purifying agent that can efficiently clean copper electrolyte and produce good purification results. Summary of the Invention

[0007] To address the problems of high impurity content in existing copper electrolytes, which are difficult to remove, and the fact that most existing purification processes suffer from high energy consumption, high risk, high pollution, and poor effectiveness, this invention provides an arsenic-antimony-bismuth purifier, as well as its specific preparation method, application method, and recycling method.

[0008] The main objective of this invention is: 1. It can be used for the efficient and thorough purification of copper electrolyte; II. The preparation process is simple and efficient; Third, it is simple and convenient to use; Fourth, it can be recycled, improving material utilization.

[0009] To achieve the above objectives, the present invention adopts the following technical solution.

[0010] A method for preparing an arsenic-antimony-bismuth purifying agent. The method includes: An antimony-containing compound is mixed with triethanolamine and stirred until homogeneous. An oxidant is added to oxidize the compound, and the mixture is then dried to obtain an arsenic-antimony-bismuth purifier.

[0011] The preparation method of the arsenic-antimony-bismuth purifier of the present invention is simple and efficient. By adjusting the pH value of the solution system with triethanolamine, the antimony compound is first converted to a certain extent. Secondly, triethanolamine has a certain reducing property and can produce a certain degree of reduction effect on the high-valence antimony in the antimony compound. Moreover, it has a certain polymerization inhibition ability. In the above reaction process, it can cooperate with the subsequent oxidant to promote the dispersion of the arsenic-antimony-bismuth purifier during the reaction.

[0012] Furthermore, for the arsenic-antimony-bismuth purifier of this invention, the composition and crystal structure significantly affect its performance, leading to substantial differences in adsorption selectivity or adsorption efficiency. In the preparation method of this invention, due to the action of triethanolamine and the oxidation of the oxidant, a mixture of defective Sb(III) and Sb(V) with many crystal defects can be formed, wherein the approximate molar ratio of Sb(III) to Sb(V) is 0.01 to 0.5:1. Therefore, the preparation process needs to be strictly controlled, and strongly alkaline substances such as sodium hydroxide and potassium hydroxide must be absolutely avoided.

[0013] As a preferred option The antimony-containing compounds include Sb₂O₄ and / or Sb₂O₃ and / or Sb₅O₂ and / or Sb₃O₆(OH) and / or Sb₆O₂. 13 .

[0014] For the purposes of this invention, all of the above antimony compounds can be effectively used in the present invention to achieve the preparation of arsenic, antimony and bismuth purifiers.

[0015] As a preferred option The molar amount of triethanolamine is 0.2 to 0.5 times the molar amount of antimony; The molar amount of the oxidant is 2 to 5 times the molar amount of antimony.

[0016] Controlling the molar amount of triethanolamine and the amount of oxidant is crucial for controlling the crystal form, crystalline state, and defect structure of the product. Specifically, for the technical solution of this invention, hydrogen peroxide is an effective oxidant, while common oxidants such as chlorine and hypochlorous acid should be avoided to prevent significant changes in the crystal structure that would prevent the desired effect from being achieved.

[0017] As a preferred option The oxidation treatment is carried out at a reaction temperature of 60–90 °C for 20–80 min.

[0018] Reaction temperature and reaction time will affect the crystal size of the product, and temperature also has a certain impact on the reaction process. Using too low or too high a temperature may result in the failure to obtain the desired product.

[0019] An arsenic-antimony-bismuth purifying agent.

[0020] The arsenic-antimony-bismuth purifier of this invention is a defective transition compound composed of a mixture of oxides of Sb(III) and Sb(V). It differs from the transition antimony oxide previously studied and filed (application number 2018116039207). The adsorption capacity and adsorption selectivity of the transition antimony oxide of this invention are different. The preparation method of the purifier is different, and the purification reaction process is different. The arsenic-antimony-bismuth purifier of this invention can form beneficial byproducts after treatment.

[0021] Application of an arsenic-antimony-bismuth purifier The arsenic-antimony-bismuth purifier is used for the purification of copper electrolyte.

[0022] Specifically, the application method is as follows: Arsenic-antimony-bismuth purifying agent was added to the initial copper electrolyte at a solid-liquid ratio of 10-15 g: 1 L. The mixture was stirred at a constant temperature of 50-70℃ for 3-5 h, and then filtered to remove the precipitate, thus obtaining the purified copper electrolyte.

[0023] A method for recovering arsenic, antimony, and bismuth purifier. The arsenic-antimony-bismuth purifying agent is used to purify copper electrolyte to form precipitate residue. The precipitate residue is then subjected to leaching and dechlorination treatments to recover antimony-containing compounds.

[0024] Regarding the technical solution of this invention, after the arsenic-antimony-bismuth purifier is used for the purification of copper electrolyte, the total antimony content of the separated precipitate is even higher than that of the arsenic-antimony-bismuth purifier used. Therefore, in actual use, the arsenic-antimony-bismuth purifier can be almost unaffected or even experience "negative loss," with the amount of arsenic-antimony-bismuth purifier increasing with use. This demonstrates that, through appropriate recycling processes, the arsenic-antimony-bismuth purifier of this invention has extremely high economic and environmental value. However, this arsenic-antimony-bismuth purifier focuses on the purification of copper electrolyte, and its effect on the treatment of polluting wastewater is relatively limited.

[0025] As a preferred option The leaching process involves mixing 0.1–3.0 mol / L hydrochloric acid with the precipitate at a solid-liquid ratio of 5–30 g / L, and leaching at 30–90 °C for 30–90 min.

[0026] The above method can be used to separate antimony compounds from impurities.

[0027] As a preferred option The dechlorination process involves mixing 0.1–3.0 mol / L ammonia water with the precipitate residue after leaching at a solid-liquid ratio of 10–100 g / L, and leaching at 20–70 °C for 30–90 min.

[0028] The above methods can effectively remove chlorine during the leaching process, forming a precipitate.

[0029] As a preferred option The recovered antimony-containing compound is used in the preparation of an arsenic-antimony-bismuth purifier.

[0030] The antimony-containing compounds recovered by this invention can be prepared again as arsenic-antimony-bismuth purifiers using the preparation method of this invention, forming a complete preparation-use-recycling cycle, which has extremely high environmental and economic value.

[0031] The beneficial effects of this invention are: This invention enables the efficient preparation of transition state special crystal forms of Sb(III) and Sb(V) compounds as arsenic-antimony-bismuth purifiers for the efficient purification of copper electrolytes, and enables the copper electrolytes to form a stable self-purification effect. At the same time, the precipitate residue generated after use can be further recycled to prepare arsenic-antimony-bismuth purifiers, which has extremely high economic and environmental value. Attached Figure Description

[0032] Figure 1 This is a SEM image of the arsenic-antimony-bismuth purifier prepared in Example 1 of the present invention; Figure 2 The image shows the XRD pattern of the arsenic-antimony-bismuth purifier prepared in Example 1 of this invention. Detailed Implementation

[0033] The present invention will be further described clearly and in detail below with reference to specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below are generally only some, not all, of the embodiments of the present invention. Therefore, all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0034] Unless otherwise specified, all raw materials used in the embodiments of the present invention are commercially available or obtainable by those skilled in the art; unless otherwise specified, all methods used in the embodiments of the present invention are methods mastered by those skilled in the art.

[0035] Example 1 An arsenic-antimony-bismuth purifying agent is prepared by the following method: Antimony-containing compound (antimony pentoxide) was mixed with triethanolamine in deionized water and oxidized using hydrogen peroxide. The solid-liquid ratio of antimony-containing compound to deionized water was 200 g / L, and the amount of triethanolamine added was 0.4 times the molar amount of antimony. The mixture was stirred and heated to 90 °C, and hydrogen peroxide was added dropwise during stirring. The amount of hydrogen peroxide added was 3 times the molar amount of antimony. The reaction time was 50 minutes, and the mixture was dried at 80 °C to obtain an arsenic-antimony-bismuth purifier. The raw material utilization rate in the preparation of this purifier is extremely high. The SEM and XRD results of the obtained purifier are shown below. Figure 1 , Figure 2 As shown, the resulting purifying agent is almost entirely transformed into an amorphous composite structure.

[0036] Example 2 An arsenic-antimony-bismuth purifying agent is prepared by the following method: Antimony-containing compound (antimony trioxide) was mixed with triethanolamine in deionized water and oxidized using hydrogen peroxide. The solid-liquid ratio of antimony-containing compound to deionized water was 50 g / L, and the amount of triethanolamine added was 0.2 times the molar amount of antimony. The mixture was stirred and heated to 80 °C, and hydrogen peroxide was added dropwise during stirring. The amount of hydrogen peroxide added was 4 times the molar amount of antimony. The reaction time was 80 minutes, and the mixture was dried at 90 °C to obtain an arsenic-antimony-bismuth purifier.

[0037] Example 3 An arsenic-antimony-bismuth purifying agent is prepared by the following method: Antimony-containing compounds (antimony pentoxide and antimony tetroxide mixed in a molar ratio of 2:1) were mixed with triethanolamine in deionized water and oxidized using hydrogen peroxide. The solid-liquid ratio of the antimony-containing compound to deionized water was 300 g / L, and the amount of triethanolamine added was 0.3 times the molar amount of antimony. The mixture was stirred and heated to 90 °C, and hydrogen peroxide was added dropwise during stirring, with the amount of hydrogen peroxide added being 1 times the molar amount of antimony. The reaction time was 70 minutes, and the mixture was dried at 90 °C to obtain an arsenic-antimony-bismuth purifier.

[0038] Example 4 An arsenic-antimony-bismuth purifying agent is prepared by the following method: An antimony-containing compound (a mixture of antimony trioxide and antimony pentoxide in a molar ratio of 0.5:1) was mixed with triethanolamine in deionized water, and then oxidized using hydrogen peroxide. The solid-liquid ratio of the antimony-containing compound to deionized water was 200 g / L, and the amount of triethanolamine added was 0.3 times the molar amount of antimony. The mixture was stirred and heated to 80 °C, and hydrogen peroxide was added dropwise during stirring, with the amount of hydrogen peroxide added being 0.5 times the molar amount of antimony. The reaction time was 80 minutes, and the mixture was dried at 90 °C to obtain an arsenic-antimony-bismuth purifier.

[0039] Example 5 An arsenic-antimony-bismuth purifying agent is prepared by the following method: Antimony-containing compound (antimony tetroxide) was mixed with triethanolamine in deionized water and oxidized using hydrogen peroxide. The solid-liquid ratio of antimony-containing compound to deionized water was 300 g / L, and the amount of triethanolamine added was 0.2 times the molar amount of antimony. The mixture was stirred and heated to 90 °C, and hydrogen peroxide was added dropwise during stirring. The amount of hydrogen peroxide added was 3 times the molar amount of antimony. The reaction time was 80 minutes, and the mixture was dried at 90 °C to obtain an arsenic-antimony-bismuth purifier.

[0040] The morphological standards of the arsenic-antimony-bismuth purifiers prepared in Examples 2 to 5 above are the same as those in Example 1. They are amorphous composite structures composed of trivalent antimony oxide and pentavalent antimony oxide, wherein the molar ratio of Sb(III) to Sb(V) is approximately (0.3 to 0.5):1.

[0041] Application and Recycling Example 1 The copper electrolyte was stirred and heated to 60°C, and the arsenic-antimony-bismuth purifying agent prepared in Example 1 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 60°C for 2 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively detected after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: The resulting precipitate was leached with hydrochloric acid at a concentration of 0.5 mol / L and a solid-liquid ratio of 5 g / L. After leaching, leaching residue and leachate were obtained. The leaching residue was dechlorinated with ammonia at a concentration of 1 mol / L and a solid-liquid ratio of 20 g / L. After filtration, antimony-containing compounds were obtained.

[0042] The obtained copper electrolyte was used to prepare cathode copper, with crude copper as the anode and stainless steel as the cathode. The electrolytic refining temperature was 60 ℃ and the current density was 300 A / m. 2 The electrolyte circulation flow rate of the electrolytic cell is 15 L / min, the total electrolysis time is 100 h, and the electrolytic copper material, namely cathode copper, is recovered after completion.

[0043] The cathode copper was continuously sampled and characterized during the preparation process. The results of the continuous sampling and characterization are shown in the table below.

[0044] It is evident that the arsenic-antimony-bismuth purifier of this invention, when used to treat copper electrolyte, can directly reduce the concentration of harmful components in the copper electrolyte, while simultaneously giving the copper electrolyte a certain degree of self-cleaning and purification ability. After 100 hours of electrolytic refining, the silver content of the resulting copper material only increases by 0.6 ppm.

[0045] The obtained antimony-containing compound was prepared according to the method of Example 1 to obtain arsenic-antimony-bismuth purifier-B1; The copper electrolyte was stirred and heated to 60°C, and arsenic-antimony-bismuth purifying agent-B1 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 60°C for 2 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively analyzed after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: It can be seen that the arsenic-antimony-bismuth purifier of the present invention has a significant effect on the purification of arsenic-antimony-bismuth in copper electrolyte. At the same time, after the antimony-containing compounds obtained from the recovery process are re-prepared as arsenic-antimony-bismuth purifiers using the preparation method of the present invention, the resulting arsenic-antimony-bismuth purifier-B1 has almost the same effect as the arsenic-antimony-bismuth purifier prepared in Example 1, with a recovery rate of 99.6% by weight.

[0046] Application and Recycling Example 2 The copper electrolyte was stirred and heated to 40°C, and the arsenic-antimony-bismuth purifying agent prepared in Example 2 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 5 g / L, and the reaction was maintained at 40°C for 1.5 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively detected after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: The resulting precipitate was leached with hydrochloric acid at a concentration of 0.5 mol / L and a solid-liquid ratio of 5 g / L. After leaching, leaching residue and leachate were obtained. The leaching residue was dechlorinated with ammonia at a concentration of 1 mol / L and a solid-liquid ratio of 20 g / L. After filtration, antimony-containing compounds were obtained.

[0047] The obtained copper electrolyte was used to prepare cathode copper, with crude copper as the anode and stainless steel as the cathode. The electrolytic refining temperature was 60 ℃ and the current density was 300 A / m. 2 The electrolyte circulation flow rate of the electrolytic cell is 15 L / min, the total electrolysis time is 100 h, and the electrolytic copper material, namely cathode copper, is recovered after completion.

[0048] The cathode copper was continuously sampled and characterized during the preparation process. The results of the continuous sampling and characterization are shown in the table below.

[0049] It is evident that the arsenic-antimony-bismuth purifier of this invention, when used to treat copper electrolyte, can directly reduce the concentration of harmful components in the copper electrolyte, while simultaneously giving the copper electrolyte a certain degree of self-cleaning and purification ability. After 100 hours of electrolytic refining, the silver content of the resulting copper material only increases by 0.6 ppm.

[0050] The obtained antimony-containing compound was prepared according to the method in Example 2 to obtain arsenic-antimony-bismuth purifier-B2; The copper electrolyte was stirred and heated to 40°C, and arsenic-antimony-bismuth purifying agent-B2 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 5 g / L, and the reaction was maintained at 40°C for 1.5 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively analyzed after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: It can be seen that the arsenic-antimony-bismuth purifier of the present invention has a significant effect on the purification of arsenic-antimony-bismuth in copper electrolyte. At the same time, after the antimony-containing compounds obtained from the recovery process are re-prepared as arsenic-antimony-bismuth purifiers using the preparation method of the present invention, the resulting arsenic-antimony-bismuth purifier-B2 has almost the same effect as the arsenic-antimony-bismuth purifier prepared in Example 2, with a recovery rate of 100.2% by weight.

[0051] Application and Recycling Example 3 The copper electrolyte was stirred and heated to 60°C, and the arsenic-antimony-bismuth purifying agent prepared in Example 3 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 60°C for 1.5 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively detected after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: The resulting precipitate was leached with hydrochloric acid at a concentration of 1 mol / L and a solid-liquid ratio of 10 g / L. After leaching, leaching residue and leaching solution were obtained. The leaching residue was dechlorinated with ammonia at a concentration of 1.5 mol / L and a solid-liquid ratio of 30 g / L. After filtration, antimony-containing compounds were obtained.

[0052] The obtained copper electrolyte was used to prepare cathode copper, with crude copper as the anode and stainless steel as the cathode. The electrolytic refining temperature was 60 ℃ and the current density was 300 A / m. 2 The electrolyte circulation flow rate of the electrolytic cell is 15 L / min, the total electrolysis time is 100 h, and the electrolytic copper material, namely cathode copper, is recovered after completion.

[0053] The cathode copper was continuously sampled and characterized during the preparation process. The results of the continuous sampling and characterization are shown in the table below.

[0054] It is evident that the arsenic-antimony-bismuth purifier of this invention, when used to treat copper electrolyte, can directly reduce the concentration of harmful components in the copper electrolyte, while simultaneously giving the copper electrolyte a certain degree of self-cleaning and purification ability. After 100 hours of electrolytic refining, the silver content of the resulting copper material only increases by 0.8 ppm.

[0055] The obtained antimony-containing compound was prepared using the method of Example 3 to obtain arsenic-antimony-bismuth purifier-B3; The copper electrolyte was stirred and heated to 60°C, and arsenic-antimony-bismuth purifying agent-B3 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 60°C for 1.5 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively analyzed after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: It can be seen that the arsenic-antimony-bismuth purifier of the present invention has a significant effect on the purification of arsenic-antimony-bismuth in copper electrolyte. At the same time, after the antimony-containing compounds obtained from the recovery process are re-prepared as arsenic-antimony-bismuth purifiers using the preparation method of the present invention, the resulting arsenic-antimony-bismuth purifier-B3 has almost the same effect as the arsenic-antimony-bismuth purifier prepared in Example 3, with a recovery rate of 98.6% by weight.

[0056] Application and Recycling Example 4 The copper electrolyte was stirred and heated to 70°C, and the arsenic-antimony-bismuth purifying agent prepared in Example 4 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 70°C for 1.5 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively detected after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: The resulting precipitate was leached with hydrochloric acid at a concentration of 0.8 mol / L and a solid-liquid ratio of 5 g / L. After leaching, leaching residue and leaching solution were obtained. The leaching residue was dechlorinated with ammonia at a concentration of 0.5 mol / L and a solid-liquid ratio of 20 g / L. After filtration, antimony-containing compounds were obtained.

[0057] The obtained copper electrolyte was used to prepare cathode copper, with crude copper as the anode and stainless steel as the cathode. The electrolytic refining temperature was 60 ℃ and the current density was 300 A / m. 2 The electrolyte circulation flow rate of the electrolytic cell is 15 L / min, the total electrolysis time is 100 h, and the electrolytic copper material, namely cathode copper, is recovered after completion.

[0058] The cathode copper was continuously sampled and characterized during the preparation process. The results of the continuous sampling and characterization are shown in the table below.

[0059] It is evident that the arsenic-antimony-bismuth purifier of this invention, when used to treat copper electrolyte, can directly reduce the concentration of harmful components in the copper electrolyte, while simultaneously giving the copper electrolyte a certain degree of self-cleaning and purification ability. After 100 hours of electrolytic refining, the silver content of the resulting copper material only increases by 0.6 ppm.

[0060] The obtained antimony-containing compound was prepared according to the method of Example 4 to obtain arsenic-antimony-bismuth purifier-B4; The copper electrolyte was stirred and heated to 70°C, and arsenic-antimony-bismuth purifying agent-B4 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 70°C for 1.5 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively analyzed after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: It can be seen that the arsenic-antimony-bismuth purifier of the present invention has a significant effect on the purification of arsenic-antimony-bismuth in copper electrolyte. At the same time, after the antimony-containing compounds obtained from the recovery process are re-prepared as arsenic-antimony-bismuth purifiers using the preparation method of the present invention, the resulting arsenic-antimony-bismuth purifier-B4 has almost the same effect as the arsenic-antimony-bismuth purifier prepared in Example 4, with a recovery rate of 99.0% by weight.

[0061] Application and Recycling Example 5 The copper electrolyte was stirred and heated to 70°C, and the arsenic-antimony-bismuth purifying agent prepared in Example 4 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 70°C for 2.5 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively detected after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: The resulting precipitate was leached with hydrochloric acid at a concentration of 0.5 mol / L and a solid-liquid ratio of 5 g / L. After leaching, leaching residue and leachate were obtained. The leaching residue was dechlorinated with ammonia at a concentration of 1 mol / L and a solid-liquid ratio of 20 g / L. After filtration, antimony-containing compounds were obtained.

[0062] The obtained copper electrolyte was used to prepare cathode copper, with crude copper as the anode and stainless steel as the cathode. The electrolytic refining temperature was 60 ℃ and the current density was 300 A / m. 2 The electrolyte circulation flow rate of the electrolytic cell is 15 L / min, the total electrolysis time is 100 h, and the electrolytic copper material, namely cathode copper, is recovered after completion.

[0063] The cathode copper was continuously sampled and characterized during the preparation process. The results of the continuous sampling and characterization are shown in the table below.

[0064] It is evident that the arsenic-antimony-bismuth purifier of this invention, when used to treat copper electrolyte, can directly reduce the concentration of harmful components in the copper electrolyte, while simultaneously giving the copper electrolyte a certain degree of self-cleaning and purification ability. After 100 hours of electrolytic refining, the silver content of the resulting copper material only increases by 0.5 ppm.

[0065] The obtained antimony-containing compound was prepared according to the method in Example 5 to obtain arsenic-antimony-bismuth purifier-B5; The copper electrolyte was stirred and heated to 70°C, and arsenic-antimony-bismuth purifier-B5 was added. The solid-liquid ratio of the purifier to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 70°C for 2.5 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively analyzed after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: It can be seen that the arsenic-antimony-bismuth purifier of the present invention has a significant effect on the purification of arsenic-antimony-bismuth in copper electrolyte. At the same time, after the antimony-containing compounds obtained from the recovery process are re-prepared as arsenic-antimony-bismuth purifiers using the preparation method of the present invention, the resulting arsenic-antimony-bismuth purifier-B5 has almost the same effect as the arsenic-antimony-bismuth purifier prepared in Example 5, with a recovery rate of 99.3% by weight.

[0066] As can be clearly seen from the above application and recycling examples 1 to 5, the arsenic-antimony-bismuth purifier of the present invention has significant uniqueness in the purification treatment of copper electrolyte. Although it is not very effective in directly removing arsenic-antimony-bismuth, when it is used in copper electrolyte, it can generate corresponding by-products so that the copper electrolyte has a certain self-purification and cleaning ability, and can keep it stable for long-term use.

[0067] Comparative Example 1 A method for reducing the silver content in cathode copper, the method comprising: 1) A mixture of antimony compounds (antimony trioxide and antimony pentoxide mechanically mixed in a molar ratio of 0.5:1) was added to the initial copper electrolyte at a solid-liquid ratio of 10 g:1 L. After stirring at a constant temperature of 60 °C for 4 h, the precipitate was removed by filtration to obtain a purified copper electrolyte. 2) Using crude copper as the anode and stainless steel as the cathode, electrolytic refining is carried out in the purified copper electrolyte obtained in step 1). The electrolytic refining temperature is 60 ℃ and the current density is 250 A / m. 2 The electrolyte circulation flow rate of the electrolytic cell is 17.5 L / min, the total electrolysis time is 300 h, and the electrolytic copper material, namely cathode copper, is recovered after completion.

[0068] The composition of the initial copper electrolyte and the purified copper electrolyte in step 1) of this embodiment is shown in the table below.

[0069] Continuous sampling and characterization were performed on the electrolytic copper material during the preparation process. The results of the continuous sampling and characterization are shown in the table below.

[0070] The characterization results above show that antimony pentoxide, as a common arsenic-antimony-bismuth purifier, also exhibits a purifying effect when mixed with antimony trioxide. It can effectively precipitate and remove arsenic-antimony-bismuth components from the initial copper electrolyte and maintains relatively good preparation results in the early stages (around 20 hours). However, after 50 hours, the silver content in the electrolytic cathode copper experiences an explosive increase, leading to a rapid decline in actual quality. This demonstrates that it cannot induce a self-purifying effect in the copper electrolyte.

[0071] Compared with the application and recycling examples 1 to 5, it can be found that after the arsenic-antimony-bismuth purifier obtained by the present invention is used, the copper electrolyte can form a stable and effective self-cleaning effect, rather than simply removing the harmful components in the copper electrolyte.

[0072] Comparative Example 2 An arsenic-antimony-bismuth purifying agent is prepared by the following method: Antimony-containing compound (antimony pentoxide) was added to deionized water and oxidized using hydrogen peroxide. The solid-liquid ratio of antimony-containing compound to deionized water was 200 g / L. The mixture was stirred and heated to 90 °C. Hydrogen peroxide was added dropwise during stirring, with the amount of hydrogen peroxide added being three times the molar amount of antimony. The reaction time was 50 minutes, and the mixture was dried at 80 °C to obtain an arsenic-antimony-bismuth purifier.

[0073] The performance verification test was carried out on the above-obtained arsenic-antimony-bismuth purifier.

[0074] The copper electrolyte was stirred and heated to 60°C, and the arsenic-antimony-bismuth purifying agent prepared in Comparative Example 2 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 60°C for 2 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively analyzed after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: It is evident that the arsenic-antimony-bismuth purifier prepared in this example has a far inferior treatment effect compared to the arsenic-antimony-bismuth purifier prepared in Example 1, and it did not exhibit the effect of imparting self-cleaning ability to the copper electrolyte in subsequent copper electrolyte treatment tests.

[0075] Comparative Example 3 An arsenic-antimony-bismuth purifying agent is prepared by the following method: Antimony-containing compound (antimony pentoxide) was mixed with ammonia in deionized water and oxidized using hydrogen peroxide. The solid-liquid ratio of antimony-containing compound to deionized water was 200 g / L, and the amount of ammonia added was 0.4 times the molar amount of antimony. The mixture was stirred and heated to 90 °C, and hydrogen peroxide was added dropwise during stirring. The amount of hydrogen peroxide added was 3 times the molar amount of antimony. The reaction time was 50 minutes, and the mixture was dried at 80 °C to obtain an arsenic-antimony-bismuth purifier.

[0076] The performance verification test was carried out on the above-obtained arsenic-antimony-bismuth purifier.

[0077] The copper electrolyte was stirred and heated to 60°C, and the arsenic-antimony-bismuth purifying agent prepared in Comparative Example 2 was added. The solid-liquid ratio of the purifying agent to the initial copper electrolyte was 10 g / L, and the reaction was maintained at 60°C for 2 hours. After filtration, purified copper electrolyte and precipitate were obtained. The content of impurity elements in the purified copper electrolyte was quantitatively analyzed after the reaction. The concentrations of each element in the copper electrolyte before and after purification are as follows: It is evident that the arsenic-antimony-bismuth purifier prepared in this example has a far inferior treatment effect compared to the arsenic-antimony-bismuth purifier prepared in Example 1, and it did not exhibit the effect of imparting self-cleaning ability to the copper electrolyte in subsequent copper electrolyte treatment tests.

Claims

1. A method for preparing an arsenic-antimony-bismuth purifying agent, characterized in that, The method includes: First, the antimony-containing compound and triethanolamine are mixed in deionized water and stirred evenly. Then, hydrogen peroxide is added dropwise during the stirring process to carry out oxidation treatment. After the oxidation treatment is completed, the mixture is dried to obtain the arsenic-antimony-bismuth purifier. The antimony-containing compounds include Sb₂O₄ and / or Sb₂O₃ and / or Sb₂O₅ and / or Sb₃O₆(OH) and / or Sb₆O₂. 13 ; The molar amount of triethanolamine is 0.2 to 0.5 times the molar amount of antimony; The molar amount of hydrogen peroxide is 2 to 5 times the molar amount of antimony; The oxidation treatment is carried out at a reaction temperature of 60–90 °C for 20–80 min. The arsenic-antimony-bismuth purifier is composed of Sb(III) oxide and Sb(V) oxide, with a molar ratio of Sb(III) to Sb(V) of (0.01 to 0.50):1, and the arsenic-antimony-bismuth purifier has an amorphous composite structure.

2. The preparation method of the arsenic-antimony-bismuth purifier according to claim 1, characterized in that, The antimony-containing compounds include Sb₂O₄ and / or Sb₂O₃ and / or Sb₂O₅.

3. The method for preparing the arsenic-antimony-bismuth purifier according to claim 1 or 2, characterized in that, The antimony-containing compound is Sb₂O₅; The solid-liquid ratio of the antimony-containing compound to deionized water is 200 g: 1 L; The molar amount of triethanolamine is 0.4 times the molar amount of antimony, the oxidation treatment temperature is 90℃, the molar amount of hydrogen peroxide is 3 times the molar amount of antimony, the reaction time is 50 min, and it is dried at 80℃.

4. An arsenic-antimony-bismuth purifying agent prepared by the method of any one of claims 1, 2 or 3.

5. The application of the arsenic-antimony-bismuth purifier as described in claim 4, characterized in that, The arsenic-antimony-bismuth purifying agent is used for the purification treatment of copper electrolyte. The arsenic-antimony-bismuth purifying agent was added to the copper electrolyte at a solid-liquid ratio of 10 g / L, and the mixture was stirred at 60°C for 2 h before filtration.

6. A method for recovering the arsenic-antimony-bismuth purifier as described in claim 4, characterized in that, The arsenic-antimony-bismuth purifying agent forms a precipitate residue after being used to purify copper electrolyte. The precipitate was leached with hydrochloric acid and then subjected to solid-liquid separation to obtain leachate and leaching residue. The leaching residue was dechlorinated with ammonia water and filtered to obtain antimony-containing compounds; The antimony-containing compound is used in the preparation of the arsenic-antimony-bismuth purifier of claim 1.

7. The method for recovering arsenic, antimony, and bismuth purifier according to claim 6, characterized in that, The leaching process involves mixing 0.1–3.0 mol / L hydrochloric acid with the precipitate at a solid-liquid ratio of 5–30 g / L, and leaching at 30–90 °C for 30–90 min.

8. The method for recovering arsenic, antimony, and bismuth purifier according to claim 6, characterized in that, The dechlorination treatment involves mixing 0.1–3.0 mol / L ammonia water with the leaching residue at a solid-liquid ratio of 10–100 g / L and treating at 20–70°C for 30–90 min.

9. The method for recovering arsenic, antimony, and bismuth purifier according to claim 6, characterized in that, The concentration of the hydrochloric acid is 0.5 mol / L, and the solid-liquid ratio of the precipitate to the hydrochloric acid is 5 g / L. The concentration of the ammonia water is 1 mol / L, and the solid-liquid ratio of the leaching residue to the ammonia water is 20 g / L.

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