Process for preparing active copper oxide by taking crude copper sulfate as raw material
By employing chemical pretreatment and calcination processes, the problems of removing impurities from crude copper sulfate and preparing active copper oxide have been solved, enabling the low-cost preparation of high-purity active copper oxide, which is suitable for fields such as catalysis, electronics, and ceramics.
Patent Information
- Application Number
- CN202511827540.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-05
- Publication Date
- 2026-02-10
AI Technical Summary
Existing technologies are difficult to effectively utilize crude copper sulfate as raw material to prepare high-purity, high-activity copper oxide, resulting in problems such as high impurity content, low product utilization, and low production efficiency, which limit its application in high-end fields.
The process involves chemical pretreatment, including reacting crude copper sulfate with H2O2, adjusting the pH with NaOH, adding ferric sulfate solution to precipitate impurity ions, adjusting the pH again with NaOH to form a precipitate, adding sodium carbonate to generate basic copper carbonate precipitate, and then calcining it in a muffle furnace to obtain copper oxide.
This technology enables the preparation of high-purity active copper oxide using inexpensive raw materials, reducing production costs, improving product utilization, simplifying operation steps, facilitating industrial production, and generating less waste and consuming less energy, thus meeting the requirements of sustainable development.
Smart Images
Figure CN121494046A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of active copper oxide preparation technology, and in particular to a process for preparing active copper oxide using crude copper sulfate as raw material. Background Technology
[0002] Activated copper oxide possesses characteristics such as large specific surface area, abundant surface defects, and excellent catalytic activity, making it widely used in areas such as lithium-ion battery cathode material modification and industrial waste gas catalytic purification. However, current industrial-grade copper oxide is mostly prepared by electrolysis or direct calcination of copper salts, resulting in problems such as high energy consumption, low purity, and insufficient activity, making it difficult to meet the stringent performance requirements of high-end applications. my country's major non-ferrous smelting enterprises have a huge copper sulfate production capacity, with crude copper sulfate (containing 85%-95% copper) being a byproduct of copper smelting and electroplating waste recovery, with an annual output exceeding one million tons. This crude copper sulfate, containing impurities such as iron, lead, and zinc, has long been exported only as a low-value-added chemical raw material, resulting in low resource utilization and environmental disposal pressure. If crude copper sulfate could be used as a raw material to prepare activated copper oxide through a green purification-controllable conversion process, not only could high-value utilization of low-value resources be achieved, but the production cost of highly active copper oxide could also be significantly reduced. In recent years, although some progress has been made in copper oxide preparation technology both domestically and internationally, systematic solutions have not yet been formed for key scientific issues such as the impurity removal mechanism, nanostructure regulation, and activity correlation of crude copper sulfate raw materials. This results in poor batch stability and low production efficiency, hindering its large-scale application in high-end fields. Therefore, developing a green preparation technology for highly active copper oxide based on crude copper sulfate has significant scientific research value and promising industrial application prospects.
[0003] This process focuses on crude copper sulfate, conducting research on a "purification-conversion-calcination" process. It aims to investigate the effects of calcination temperature and holding time on the product's crystal structure, specific surface area, and catalytic activity, ultimately developing a process technology route and research results applicable to actual production. Based on material characteristic studies, this process employs a unique chemical pretreatment technique, effectively addressing issues such as high impurity content and low product utilization in crude copper sulfate. Furthermore, it can provide technical reference and assistance to other non-ferrous metal smelting enterprises in China. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide a process for preparing active copper oxide using crude copper sulfate as raw material with low raw material cost and high product utilization rate.
[0005] To address the above problems, the present invention provides a process for preparing activated copper oxide using crude copper sulfate as raw material, characterized by comprising the following steps: S1: The crude copper sulfate aqueous solution is reacted with a certain amount of H2O2, and then the pH is adjusted for the first time with NaOH solution; ferric sulfate solution is added to the obtained leachate and heated and stirred, and then the pH is adjusted for the second time with NaOH solution to precipitate the impurity ions, thus obtaining a refined copper sulfate solution. S2: A certain amount of sodium carbonate precipitant is added to the refined copper sulfate solution obtained in step S1, and basic copper carbonate precipitate is generated after the reaction. S3: The basic copper carbonate precipitate obtained in step S2 is washed multiple times, dried, and then calcined in a muffle furnace to produce copper oxide.
[0006] In step S1 above, the volume ratio of crude copper sulfate aqueous solution to H2O2 is 20:80; the reaction temperature of crude copper sulfate aqueous solution and H2O2 is 50℃, and the reaction time is 30min; after the first pH adjustment of NaOH solution, the pH value is in the range of 3.5~4.0; after the second pH adjustment of NaOH solution, the pH value is in the range of 8.0~9.0.
[0007] In step S1 above, the added ferric sulfate solution is: 2 mL of 10 wt% ferric sulfate solution; the heating temperature is 30℃; and the stirring time is 30 min.
[0008] In step S1 above, the reaction process for removing impurities from crude copper sulfate is as follows: (1) Oxidation reaction of Fe²⁺: H₂O₂ oxidizes Fe²⁺ to Fe³⁺ under acidic conditions; Ionic equation: 2Fe²⁺ + H₂O₂ + 2H⁺ = 2Fe³⁺ + 2H₂O (2) First pH adjustment: Fe³⁺ hydrolyzes within this pH range to form Fe(OH)₃ precipitate; Ionic equation: Fe³⁺ + 3H₂O ⇌ Fe(OH)₃↓ + 3H⁺ (3) Coprecipitation reaction after adding ferric sulfate solution: Fe³⁺ coprecipitates with possible impurity ions at pH 8.0~9.0; (4) Second pH adjustment: to further form hydroxide precipitates of the remaining impurity ions, while avoiding Cu²⁺ precipitation.
[0009] In step S2 above, the reaction process for the formation of basic copper carbonate is as follows: Copper ions undergo a hydrolysis reaction with carbonate ions: 2CuSO4 + 2Na2CO3 + H2O = Cu2(OH)2CO3↓ + 2Na2SO4 + CO2↑.
[0010] In step S2 above, the mass ratio of refined copper sulfate solution to sodium carbonate precipitant is 5:1 to 5.3:1; the reaction temperature is 60-70℃; and the reaction time is 1 hour.
[0011] In step S3 above, the basic copper carbonate is washed until the pH is neutral; the washed basic copper carbonate is placed in a drying oven for drying at a temperature of 80~100℃ for 12 hours; the calcination temperature in the muffle furnace is set to 300~500℃ for 2 hours, and the heating rate during the calcination process is controlled at 10℃ / min.
[0012] In step S3 above, the reaction process of basic copper carbonate is as follows: Cu2(OH)2CO3→ 2CuO + H2O + CO2↑.
[0013] This invention uses crude copper sulfate as a raw material to prepare activated copper oxide. Crude copper sulfate is a relatively inexpensive industrial raw material with wide availability. Using it as a raw material for preparing activated copper oxide can reduce production costs and improve economic efficiency. Secondly, the process of preparing activated copper oxide using crude copper sulfate is relatively simple, requiring no complex equipment or cumbersome operating steps, and is easy to implement for industrial production. In addition, the prepared activated copper oxide has a high specific surface area and porosity, high activity, and good application performance in catalysis, electronics, ceramics and other fields. Finally, the preparation process generates less waste, has less environmental pollution, and consumes less energy, which meets the requirements of sustainable development. Attached Figure Description
[0014] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.
[0015] Figure 1 This is a process flow diagram of an embodiment of the present invention. Detailed Implementation
[0016] The present invention is not limited to the following embodiments, and the specific implementation can be determined according to the technical solution of the present invention and the actual situation.
[0017] Example 1: As Figure 1 As shown in the figure, this invention discloses a process for preparing activated copper oxide using crude copper sulfate as raw material, comprising the following steps: S1: React the crude copper sulfate aqueous solution with a certain amount of H2O2, and then adjust the pH for the first time with NaOH solution; add ferric sulfate solution to the resulting solution and heat and stir, and then adjust the pH for the second time with NaOH solution to precipitate impurity ions and obtain refined copper sulfate solution; S2: A certain amount of sodium carbonate precipitant is added to the refined copper sulfate solution obtained in step S1, and basic copper carbonate precipitate is generated after the reaction. S3: The basic copper carbonate precipitate obtained in step S2 is washed multiple times, dried, and then calcined in a muffle furnace to produce copper oxide.
[0018] In step S1, the aqueous solution of crude copper sulfate is reacted with a certain amount of H2O2, and then the pH is adjusted for the first time with NaOH solution. After stirring, the resulting solution is filtered, and a certain amount of antimony and bismuth in the leaching residue is further recovered. Ferric sulfate solution is added to the resulting leachate and heated and stirred. Then the pH is adjusted for the second time with NaOH solution to precipitate the impurity ions and obtain a refined copper sulfate solution. At the same time, the filtered arsenic iron slag is calcined.
[0019] In step S1, the volume ratio of crude copper sulfate aqueous solution to H2O2 is 20:80; the reaction temperature of crude copper sulfate aqueous solution and H2O2 is 50℃, and the reaction time is 30min; after the first pH adjustment of NaOH solution, the pH value is in the range of 3.5~4.0; after the second pH adjustment of NaOH solution, the pH value is in the range of 8.0~9.0.
[0020] In step S1, the added ferric sulfate solution is: 2 mL of 10 wt% ferric sulfate solution; the heating temperature is 30 °C; and the stirring time is 30 min.
[0021] In step S1, the reaction process for removing impurities from crude copper sulfate is as follows: (1) Oxidation reaction of Fe²⁺ (50℃): H₂O₂ oxidizes Fe²⁺ to Fe³⁺ under acidic conditions; Ionic equation: 2Fe²⁺ + H₂O₂ + 2H⁺ = 2Fe³⁺ + 2H₂O (2) First pH adjustment (3.5~4.0): Fe³⁺ hydrolyzes within this pH range to form Fe(OH)₃ precipitate; Ionic equation: Fe³⁺ + 3H₂O ⇌ Fe(OH)₃↓ + 3H⁺ (3) Coprecipitation reaction after adding ferric sulfate solution (30℃): Fe³⁺ coprecipitates with possible impurity ions (such as Al³⁺, Zn²⁺, etc.) at pH 8.0~9.0; Example ionic equation (using Al³⁺ as an example): Al³⁺ + 3OH⁻ = Al(OH)₃↓ Fe³⁺ + 3OH⁻ = Fe(OH)₃↓ (4) Second pH adjustment (8.0~9.0): to further induce the remaining impurity ions (such as Al³⁺, Zn²⁺, etc.) to form hydroxide precipitates, while avoiding Cu²⁺ precipitation (Cu²⁺ will precipitate in large quantities when pH>9).
[0022] In step S2, the reaction process for the formation of basic copper carbonate is as follows: Copper ions undergo a hydrolysis reaction with carbonate ions: 2CuSO4 + 2Na2CO3 + H2O = Cu2(OH)2CO3↓ + 2Na2SO4 + CO2↑.
[0023] In step S2, the mass ratio of refined copper sulfate solution to sodium carbonate precipitant is 5:1 to 5.3:1; the reaction temperature is 60-70℃; and the reaction time is 1 hour.
[0024] In step S3, the basic copper carbonate is washed until the pH is neutral; the washed basic copper carbonate is placed in a drying oven for drying at a temperature of 80~100℃ for 12 hours; the calcination temperature in the muffle furnace is set to 300~500℃ for 2 hours, and the heating rate during the calcination process is controlled at 10℃ / min.
[0025] In step S3, the reaction process of basic copper carbonate is as follows: Cu2(OH)2CO3→ 2CuO + H2O + CO2↑.
[0026] This invention uses crude copper sulfate as a raw material to prepare activated copper oxide. Crude copper sulfate is a relatively inexpensive industrial raw material with wide availability. Using it as a raw material for preparing activated copper oxide can reduce production costs and improve economic efficiency. Secondly, the process of preparing activated copper oxide from crude copper sulfate is relatively simple, requiring no complex equipment or cumbersome operating procedures, making it easy to achieve industrial-scale production. Furthermore, the prepared activated copper oxide has a high specific surface area and porosity, exhibiting high activity and good application performance in catalysis, electronics, ceramics, and other fields. Finally, the preparation process generates relatively little waste, resulting in minimal environmental pollution, while also consuming less energy, thus meeting the requirements of sustainable development.
[0027] Example 2: This embodiment of the invention discloses a process for preparing activated copper oxide using crude copper sulfate as raw material, comprising: A. Add crude copper sulfate aqueous solution to the reaction vessel and react with 2 ml of H2O2 at 50℃ for 30 min. Then adjust the pH with NaOH solution to a value between 3.5 and 4.0. Add 2 mL of 10 wt% ferric sulfate solution dropwise to the above solution and stir at 30℃ for 30 min. Then adjust the pH with NaOH solution to a value between 8.0 and 9.0 to precipitate impurity ions. B. Add 2g of sodium carbonate precipitant to refined copper sulfate, control the reaction temperature at 60-70℃, and react for 1 hour to generate basic copper carbonate precipitate. C. The generated basic copper carbonate is washed multiple times; the washed basic copper carbonate is then placed in a drying oven at a temperature of 80~100℃ for 12 hours to dry.
[0028] D. Place the dried basic copper carbonate into a muffle furnace for calcination. The calcination temperature is set to 300~500℃, the heating rate is 10℃ / min, the final temperature is 350℃, and the calcination time is 2h.
[0029] In this embodiment, the impurity removal rate of crude copper sulfate was 97%, the purity of the prepared active copper oxide was 99.05%, and the calculated copper recovery rate was 90.25%.
[0030] Example 3: This embodiment of the invention discloses a process for preparing activated copper oxide using crude copper sulfate as raw material, comprising: A. Adding an aqueous solution of crude copper sulfate to a reaction vessel and reacting it with 3 ml of H2O2 at 50°C for 30 min, then adjusting the pH with NaOH solution to a pH value in the range of 3.5~4.0; adding 2 mL of 10 wt% ferric sulfate solution dropwise to the above solution, stirring at 30°C for 30 min, then adjusting the pH with NaOH solution to a pH value of 8.0~9.0, so that impurity ions form a precipitate; B. Add 3g of sodium carbonate precipitant to refined copper sulfate, control the reaction temperature at 60-70℃, and react for 1 hour to generate basic copper carbonate precipitate. C. The generated basic copper carbonate is washed multiple times; the washed basic copper carbonate is then placed in a drying oven at a temperature of 80~100℃ for 12 hours to dry.
[0031] D. Place the dried basic copper carbonate into a muffle furnace for calcination. Set the calcination temperature to 300~500℃, the heating rate to 15℃ / min, the final temperature to 360℃, and the calcination time to 2h.
[0032] In this embodiment, the impurity removal rate of crude copper sulfate was 98%, the purity of the prepared active copper oxide was 99.37%, and the copper recovery rate was calculated to be 91.42%.
[0033] Example 4: This embodiment of the invention discloses a process for preparing activated copper oxide using crude copper sulfate as raw material, comprising: A. Add crude copper sulfate aqueous solution to the reaction vessel and react with 4 ml of H2O2 at 50℃ for 30 min. Then adjust the pH with NaOH solution to a value between 3.5 and 4.0. Add 2 mL of 10 wt% ferric sulfate solution dropwise to the above solution and stir at 30℃ for 30 min. Then adjust the pH with NaOH solution to a value between 8.0 and 9.0 to precipitate impurity ions. B. Add 4g of sodium carbonate precipitant to refined copper sulfate, control the reaction temperature at 60-70℃, and react for 1 hour to generate basic copper carbonate precipitate. C. The generated basic copper carbonate is washed multiple times; the washed basic copper carbonate is then placed in a drying oven at a temperature of 80~100℃ for 12 hours to dry.
[0034] D. Place the dried basic copper carbonate into a muffle furnace for calcination. The calcination temperature is set to 300~500℃, the heating rate is 10℃ / min, the final temperature is 400℃, and the calcination time is 2h.
[0035] In this embodiment, the impurity removal rate of crude copper sulfate was 98.5%, the purity of the prepared active copper oxide was 99.95%, and the copper recovery rate was calculated to be 91.37%.
Claims
1. A process for preparing activated copper oxide from crude copper sulfate, characterized in that, Includes the following steps: S1: React the crude copper sulfate aqueous solution with a certain amount of H2O2, and then adjust the pH for the first time with NaOH solution; add ferric sulfate solution to the resulting solution and heat and stir, and then adjust the pH for the second time with NaOH solution to precipitate impurity ions and obtain refined copper sulfate solution; S2: A certain amount of sodium carbonate precipitant is added to the refined copper sulfate solution obtained in step S1, and basic copper carbonate precipitate is generated after the reaction. S3: The basic copper carbonate precipitate obtained in step S2 is washed multiple times, dried, and then calcined in a muffle furnace to produce copper oxide.
2. The process for preparing activated copper oxide from crude copper sulfate as raw material according to claim 1, characterized in that, In step S1, the volume ratio of crude copper sulfate aqueous solution to H2O2 is 20:80; the reaction temperature of crude copper sulfate aqueous solution and H2O2 is 50℃, and the reaction time is 30min; after the first pH adjustment of NaOH solution, the pH value is in the range of 3.5~4.0; after the second pH adjustment of NaOH solution, the pH value is in the range of 8.0~9.
0.
3. A process for preparing activated copper oxide from crude copper sulfate as a raw material according to claim 1 or 2, characterized in that, In step S1, the added ferric sulfate solution is: 2 mL of 10 wt% ferric sulfate solution; the heating temperature is 30 °C; and the stirring time is 30 min.
4. The process for preparing activated copper oxide from crude copper sulfate as raw material according to claim 3, characterized in that, In step S1, the reaction process for removing impurities from crude copper sulfate is as follows: (1) Oxidation reaction of Fe²⁺: H₂O₂ oxidizes Fe²⁺ to Fe³⁺ under acidic conditions; Ionic equation: 2Fe²⁺ + H₂O₂ + 2H⁺ = 2Fe³⁺ + 2H₂O (2) First pH adjustment: Fe³⁺ hydrolyzes within this pH range to form Fe(OH)₃ precipitate; Ionic equation: Fe³⁺ + 3H₂O ⇌ Fe(OH)₃↓ + 3H⁺ (3) Coprecipitation reaction after adding ferric sulfate solution: Fe³⁺ coprecipitates with possible impurity ions at pH 8.0~9.0; (4) Second pH adjustment: to further form hydroxide precipitates of the remaining impurity ions, while avoiding Cu²⁺ precipitation.
5. The process for preparing activated copper oxide from crude copper sulfate as raw material according to claim 1, characterized in that, In step S2, the reaction process for the formation of basic copper carbonate is as follows: Copper ions undergo a hydrolysis reaction with carbonate ions: 2CuSO4 + 2Na2CO3 + H2O = Cu2(OH)2CO3↓ + 2Na2SO4 + CO2↑.
6. The process for preparing activated copper oxide from crude copper sulfate as raw material according to claim 1, characterized in that, In step S2, the mass ratio of refined copper sulfate solution to sodium carbonate precipitant is 5:1 to 5.3:1; the reaction temperature is 60-70℃; and the reaction time is 1 hour.
7. The process for preparing activated copper oxide from crude copper sulfate as raw material according to claim 1, characterized in that, In step S3, the basic copper carbonate is washed until the pH is neutral; the washed basic copper carbonate is placed in a drying oven for drying at a temperature of 80~100℃ for 12 hours; the calcination temperature in the muffle furnace is set to 300~500℃ for 2 hours, and the heating rate during the calcination process is controlled at 10℃ / min.
8. The process for preparing activated copper oxide from crude copper sulfate as raw material according to claim 1, characterized in that, In step S3, the reaction process of basic copper carbonate is as follows: Cu2(OH)2CO3→ 2CuO + H2O + CO2↑.