阅读说明：本技术 一种从氧化铜钴矿萃铜余液中制备高品质氧化钴的方法 (Method for preparing high-quality cobalt oxide from copper extraction raffinate of copper oxide cobalt ore ) 是由 詹光 舒方霞 李辉 于 2021-10-19 设计创作，主要内容包括：本发明属于有色冶金湿法冶金领域,涉及一种从氧化铜钴矿萃铜余液中提取钴并制备高品质氧化钴的方法。方法包括：氧化钙除铁、铝；氧化镁除铜；氟化钠除钙、镁；萃取剂P-(2)O-(4)的皂化及配制；萃取除杂；草酸钴前躯体制备；高品质氧化钴制备。本发明针对氧化铜钴矿萃铜余液钴提取及产品制备工艺杂质含量高、钴损失较多的问题,该方法增加深度除杂工艺步骤,使用沉淀法制备草酸钴前躯体,煅烧成为高品质氧化钴。具有除杂彻底,钴回收率高的特点。(The invention belongs to the field of nonferrous metallurgy hydrometallurgy, and relates to a method for extracting cobalt from copper raffinate of copper oxide cobalt ores and preparing high-quality cobalt oxide. The method comprises the following steps: removing iron and aluminum from calcium oxide; removing copper from magnesium oxide; removing calcium and magnesium from sodium fluoride; extractant P 2 O 4 Saponification and preparation; extracting and removing impurities; preparing a cobalt oxalate precursor; and preparing high-quality cobalt oxide. Aiming at the problems of high impurity content and more cobalt loss in the extraction of residual cobalt in copper extraction of copper oxide cobalt ore and the product preparation process, the method adds a deep impurity removal process step, prepares a cobalt oxalate precursor by using a precipitation method, and calcines the precursor to obtain the high-quality cobalt oxide. Has the characteristics of thorough impurity removal and high cobalt recovery rate.)

1. A method for extracting cobalt from copper extraction raffinate of copper oxide cobalt ore and preparing high-quality cobalt oxide is characterized by comprising the following steps:

step 1, removing iron and aluminum from calcium oxide: adding a certain amount of calcium oxide slurry with the mass concentration of 50-80% into the copper extraction raffinate of the copper oxide cobalt ore at normal temperature, adjusting the pH value to completely precipitate iron and aluminum, and filtering to separate the solution from iron and aluminum slag;

step 2, removing copper by magnesium oxide: adding a certain amount of magnesium oxide slurry with the mass concentration of 50-80% into the solution obtained in the step (1) at normal temperature, adjusting the pH value to completely precipitate copper ions, and filtering to obtain impurity-removing liquid and copper hydroxide precipitate;

step 3, removing calcium and magnesium from sodium fluoride: heating the impurity-removed solution obtained in the step 2 to 90-95 ℃, adding a certain amount of sodium fluoride to react for 30-60min, filtering and cooling to obtain impurity-removed solution and calcium-magnesium fluoride precipitate;

step 4, extracting agent P₂O₄Saponification and preparation: taking a certain amount of P₂O₄Saponifying, and preparing an extraction organic phase with a certain concentration with sulfonated kerosene;

and step 5, extraction and impurity removal: adjusting the pH value to a proper value by using 1moL/L dilute sulfuric acid, fully mixing and stirring the impurity-removed liquid obtained in the step 3 and the extracted organic phase obtained in the step 4, and separating liquid to obtain raffinate and an organic phase;

step 6, preparing a cobalt oxalate precursor: directly adding a certain amount of oxalic acid solid into the raffinate obtained in the step 5, reacting for 3-4 hours, controlling the pH value =0.9-1.1, filtering and drying to obtain a cobalt oxalate product;

step 7, preparing high-quality cobalt oxide: and (4) calcining the cobalt oxalate precursor obtained in the step (6) at 500 ℃ for 2-3 hours to obtain a high-quality cobalt oxide product.

2. The method for extracting cobalt from the copper raffinate of the copper cobalt oxide ore and preparing high-quality cobalt oxide according to claim 1, wherein the calcium oxide slurry in the step 1 is adjusted to have a pH = 3.5-4.5.

3. The method for extracting cobalt from the copper raffinate of the copper cobalt oxide ore and preparing high-quality cobalt oxide according to claim 1, wherein the magnesium oxide slurry in the step 2 is adjusted to pH = 5-5.7.

4. The method for extracting cobalt from the copper raffinate of the copper oxide cobalt ore and preparing high-quality cobalt oxide according to claim 1, wherein the amount of the sodium fluoride added in the step 3 is 1 to 3 times of the amount of the calcium and magnesium ions in the solution.

5. The method for extracting cobalt from the copper raffinate of the copper-cobalt oxide ore and preparing high-quality cobalt oxide according to claim 1, wherein the saponification rate of the extractant in the step 4 is 50-80%, and the mass concentration of the extractant is 10-30%.

6. The method for extracting cobalt from the copper raffinate of the copper-cobalt oxide ore and preparing high-quality cobalt oxide according to claim 1, wherein the step 5 is suitable for pH conditions of 2.5-3.5, and the extraction stages are 1-3 stages compared with O/A1: 1-1: 2.

7. The method for extracting cobalt from the copper raffinate of the copper cobalt oxide ore and preparing high-quality cobalt oxide according to claim 1, wherein the cobalt oxide product obtained in the step 7 is cobaltosic oxide.

Technical Field

The invention belongs to the field of nonferrous metallurgy hydrometallurgy, and relates to a method for extracting cobalt from copper raffinate of copper oxide cobalt ores and preparing high-quality cobalt oxide.

Background

Cobalt is a very important strategic metal, has excellent physical and chemical properties, good wear resistance, high strength, corrosion resistance and strong magnetism, and is widely applied to the fields of new energy, aerospace, mechanical manufacturing, chemical engineering, medical treatment and the like. Cobalt oxide is a common cobalt-containing product in industry, is used as a positive electrode material of a cobalt lithium battery, is used as a catalyst in chemical industry, and is also used as a coloring agent of colors such as glass, enamel, ceramics, magnetic materials, an adhesive, sky blue, cobalt green and the like, and a trace element nutrient for livestock.

Along with economic development, the demand of cobalt resources on the global scale is getting larger and larger, common cobalt minerals in nature are mainly laterite nickel cobalt ore and copper oxide cobalt ore, and the copper oxide cobalt ore is taken as one of important cobalt sources and is characterized by high copper content, low cobalt content and high silicon content. The main current methods for treating copper oxide cobalt ores are flotation, pyrogenic and wet processes. The wet treatment process has become a mainstream process, and the common process comprises copper-cobalt ore-ore dressing and grinding-reduction leaching-copper extraction-neutralization deferrization-cobalt precipitation, wherein the raffinate after copper extraction contains cobalt ions, and the process of impurity removal-cobalt precipitation is usually adopted to produce cobalt salt and cobalt compounds. The precipitant used in the cobalt precipitation process is generally H₂S, sulfide, metal oxide, sodium salt, oxalic acid, etc. H₂S has toxicity, is harmful to human health and easily causes environmental pollution. Sodium salt such as Na₂CO₃And NaOH and the like are strong in alkalinity, so that partial pH of the solution is easily high, other impurity ions and cobalt ions are precipitated together and enter the slag, the grade of cobalt in the cobalt-precipitated slag is reduced, and meanwhile, Na salts can be brought into a system to form Na⁺Inconvenient to handle, Na⁺When the content is too large, the actual production is adversely affected. MgO is alkalescent, is relatively safer to use, but is easy to cause MgO inclusion in products, and reduces the quality of cobalt products.

Production practices show that the cobalt product extracted and prepared from the copper raffinate of the copper oxide cobalt ore by using the traditional wet method has high impurity content and more cobalt loss in the process, so that the problems need to be solved by changing impurity removal process conditions and routes.

Disclosure of Invention

The invention provides a method for extracting cobalt from copper extraction raffinate of copper oxide cobalt ore and preparing high-quality cobalt oxide aiming at the problems of high impurity content and more cobalt loss in the processes of extracting the cobalt from the copper extraction raffinate of the copper oxide cobalt ore and preparing products. Has the characteristics of thorough impurity removal and high cobalt recovery rate.

In order to achieve the purpose, the invention adopts a technical scheme that.

A method for extracting cobalt from copper extraction raffinate of copper oxide cobalt ore and preparing high-quality cobalt oxide comprises the following steps:

step 1, removing iron and aluminum from calcium oxide: at normal temperature, adding a certain amount of calcium oxide slurry with the mass concentration of 50-80% into the copper extraction raffinate of the copper oxide cobalt ore, adjusting the pH value to completely precipitate iron and aluminum, and filtering to separate the solution from iron and aluminum slag.

Step 2, removing copper by magnesium oxide: and (2) at normal temperature, adding a certain amount of magnesium oxide slurry with the mass concentration of 50-80% into the solution obtained in the step (1), adjusting the pH value to completely precipitate copper ions, and filtering to obtain impurity-removing liquid and copper hydroxide precipitate.

Step 3, removing calcium and magnesium from sodium fluoride: and (3) heating the impurity-removed liquid obtained in the step (2) to 90-95 ℃, adding a certain amount of sodium fluoride to react for 30-60min, filtering and cooling to obtain the impurity-removed liquid and calcium-magnesium fluoride precipitate.

Step 4, extracting agent P₂O₄Saponification and preparation: taking a certain amount of P₂O₄Saponifying, and mixing with sulfonated kerosene to obtain an organic phase.

And step 5, extraction and impurity removal: and (3) adjusting the pH value to a proper value by using 1moL/L dilute sulfuric acid, fully mixing and stirring the impurity-removed liquid obtained in the step (3) and the extracted organic phase obtained in the step (4), and separating the liquid to obtain raffinate and an organic phase.

Step 6, preparing a cobalt oxalate precursor: and (3) directly adding a certain amount of oxalic acid solid into the raffinate obtained in the step (5), reacting for 3-4 hours, controlling the pH value =0.9-1.1, filtering and drying to obtain a cobalt oxalate product.

Step 7, preparing high-quality cobalt oxide: and (4) calcining the cobalt oxalate precursor obtained in the step (6) at 500 ℃ for 2-3 hours to obtain a high-quality cobalt oxide product.

Further, the calcium oxide slurry in step 1 is adjusted to pH = 3.5-4.5.

Further, the magnesium oxide slurry in step 2 is adjusted to pH = 5-5.7.

Further, in the step 3, the adding amount of the sodium fluoride is 1-3 times of the amount of the calcium and magnesium ions in the solution.

Further, in the step 4, the saponification rate of the extracting agent is 50-80%, and the mass concentration of the extracting agent is 10-30%.

Further, the step 5 is suitable for the pH condition of 2.5-3.5, and the extraction grade number is 1-3 compared with the O/A ratio of 1:1-1: 2.

Further, the cobalt oxide product obtained in the step 7 contains cobaltosic oxide as a component.

Compared with the prior art, the invention has the beneficial effects of.

(1) The cobalt loss rate is low, and the cobalt loss of the whole process is 1.2 percent.

(2) The impurity content of the cobalt oxide product is low, the total impurity content is below 2%, and the cobalt oxide content can reach more than 98%.

(3) The whole process is basically carried out at normal temperature, and the energy consumption is low.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

A method for extracting cobalt from copper extraction raffinate of copper oxide cobalt ore and preparing high-quality cobalt oxide comprises the following steps:

step 1, removing iron and aluminum from calcium oxide: at normal temperature, adding a certain amount of calcium oxide slurry with the mass concentration of 50-80% into the copper extraction raffinate of the copper oxide cobalt ore, adjusting the pH value to completely precipitate iron and aluminum, and filtering to separate the solution from iron and aluminum slag.

Step 2, removing copper by magnesium oxide: and (2) at normal temperature, adding a certain amount of magnesium oxide slurry with the mass concentration of 50-80% into the solution obtained in the step (1), adjusting the pH value to completely precipitate copper ions, and filtering to obtain impurity-removing liquid and copper hydroxide precipitate.

Step 3, removing calcium and magnesium from sodium fluoride: and (3) heating the impurity-removed liquid obtained in the step (2) to 90-95 ℃, adding a certain amount of sodium fluoride to react for 30-60min, filtering and cooling to obtain the impurity-removed liquid and calcium-magnesium fluoride precipitate.

Step 4, extracting agent P₂O₄Saponification and preparation: taking a certain amount of P₂O₄Saponifying, and mixing with sulfonated kerosene to obtain an organic phase.

And step 5, extraction and impurity removal: and (3) adjusting the pH value to a proper value by using 1moL/L dilute sulfuric acid, fully mixing and stirring the impurity-removed liquid obtained in the step (3) and the extracted organic phase obtained in the step (4), and separating the liquid to obtain raffinate and an organic phase.

Step 6, preparing a cobalt oxalate precursor: and (3) directly adding a certain amount of oxalic acid solid into the raffinate obtained in the step (5), reacting for 3-4 hours, controlling the pH value =0.9-1.1, filtering and drying to obtain a cobalt oxalate product.

Step 7, preparing high-quality cobalt oxide: and (4) calcining the cobalt oxalate precursor obtained in the step (6) at 500 ℃ for 2-3 hours to obtain a high-quality cobalt oxide product.

Further, the calcium oxide slurry in step 1 is adjusted to pH = 3.5-4.5.

Further, the magnesium oxide slurry in step 2 is adjusted to pH = 5-5.7.

Further, in the step 3, the adding amount of the sodium fluoride is 1-3 times of the amount of the calcium and magnesium ions in the solution.

Further, in the step 4, the saponification rate of the extracting agent is 50-80%, and the mass concentration of the extracting agent is 10-30%.

Further, the step 5 is suitable for the pH condition of 2.5-3.5, and the extraction grade number is 1-3 compared with the O/A ratio of 1:1-1: 2.

Further, the cobalt oxide product obtained in the step 7 contains cobaltosic oxide as a component.

In the following scheme, the content of each metal ion in the copper raffinate of the copper oxide cobalt ore is as follows: 21.8% of aluminum, 14.01% of magnesium, 8.79% of cobalt, 8.57% of manganese, 5.12% of iron, 4.79% of calcium, 3.59% of zinc and 3.47% of copper, and the initial pH value is 1.5.

Example 1.

Measuring 30 mL of copper extraction raffinate, adding 70% calcium oxide slurry, stirring at normal temperature until the end point pH is 4.0, taking out and filtering; adding 70% magnesium oxide slurry into the filtered solution until the pH value is 5.5, and immediately filtering; adding 1.75 times of the filtrateHeating and stirring the calcium-magnesium equivalent sodium fluoride powder at 95 ℃ for 60 minutes, and filtering to obtain filtrate; adjusting the pH of the filtrate to 3.0 with 1moL/L dilute sulfuric acid, the saponification rate to 70%, and the concentration to 20% P₂O₄Mixing the extractants 1:1, stirring for 5 minutes at normal temperature, and standing for liquid separation; adding oxalic acid into the raffinate obtained in the previous step to adjust the pH value to 1.0, stirring for 3 hours at normal temperature, filtering, and drying the filtered cobalt oxalate at 70 ℃ to remove water; and calcining the prepared cobalt oxalate powder at 500 ℃ for 3 hours, and taking out, cooling and packaging.

By the process, the cobaltosic oxide product has the cobaltosic oxide content of 98.65 percent, the total impurity content of 1.35 percent and the total cobalt recovery rate of 98.9 percent.

Example 2.

Measuring 50 mL of copper extraction raffinate, adding 70% calcium oxide slurry, stirring at normal temperature until the end point pH is 3.5, taking out and filtering; adding 70% magnesium oxide slurry into the filtered solution until the pH value is 5.7, and immediately filtering; adding 2 times of calcium and magnesium equivalent sodium fluoride powder into the filtrate, heating and stirring at 90 ℃ for 30 minutes, and filtering to obtain filtrate; adjusting the pH of the filtrate to 2.5 with 1mol/L dilute sulfuric acid, the saponification rate to 50%, and the concentration to 20% P₂O₄Extracting agent 1:1, mixing, stirring for 10 minutes at normal temperature, and standing for liquid separation; adding oxalic acid into the raffinate obtained in the previous step to adjust the pH value to 1.1, stirring for 3 hours at normal temperature, filtering, and drying the filtered cobalt oxalate at 70 ℃ to remove water; and calcining the prepared cobalt oxalate powder at 500 ℃ for 3 hours, and taking out, cooling and packaging.

By the process, the cobaltosic oxide product is obtained, wherein the cobaltosic oxide content is 98.71%, the total impurity content is 1.29%, and the total cobalt recovery rate is 97.4%.

Example 3.

Measuring 100ml of copper extraction raffinate, adding 70% calcium oxide slurry, stirring at normal temperature until the end point pH is 4.5, taking out and filtering; adding 70% magnesium oxide slurry into the filtered solution until the pH value is 5.0, and immediately filtering; adding 1.75 times of calcium and magnesium equivalent sodium fluoride powder into the filtrate, heating and stirring at 95 ℃ for 60 minutes, and filtering to obtain filtrate; adjusting the pH of the filtrate to 3.5 with 1mol/L dilute sulfuric acid, the saponification rate to 80%, and the concentration to 20% P₂O₄The extracting agent is prepared according to the following ratio of O/A1:2, mixing, stirring for 5 minutes at normal temperature, and standing for liquid separation; adding oxalic acid into the raffinate obtained in the previous step to adjust the pH value to 0.9, stirring for 4 hours at normal temperature, filtering, and drying the filtered cobalt oxalate at 70 ℃ to remove water; and calcining the prepared cobalt oxalate powder at 500 ℃ for 2 hours, and taking out, cooling and packaging.

By the process, the cobaltosic oxide product has the cobaltosic oxide content of 98.97%, the total impurity content of 1.03% and the total cobalt recovery rate of 98.3%.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.