阅读说明：本技术 一种钴矿浸出液中二价铁的氧化工艺 (Oxidation process for ferrous iron in cobalt ore leaching solution ) 是由 许开华 李炳忠 宁超 毕凡 许东伟 于 2020-11-12 设计创作，主要内容包括：本发明公开了一种钴矿浸出液中二价铁的氧化工艺,该工艺为将钴矿浸出液加热至60℃-70℃,加入二氧化锰矿进行搅拌混合,控制溶液的pH值小于1.5,氧化反应时间为20min～1h,当溶液中的Fe~(2+)含量低于0.05g/L时,氧化反应结束。与现有技术相比,本发明采用二氧化锰矿将钴矿浸出液中的Fe~(2+)氧化成Fe~(3+),大幅度缩短反应时间,且二氧化锰矿不属于危化品,从而避免操作与存贮的安全问题。(The invention discloses an oxidation process of ferrous iron in cobalt ore leachate, which comprises the steps of heating the cobalt ore leachate to 60-70 ℃, adding manganese dioxide ore, stirring and mixing, controlling the pH value of the solution to be less than 1.5, controlling the oxidation reaction time to be 20 min-1 h, and reacting when Fe in the solution is 2+ When the content is less than 0.05g/L, the oxidation reaction is ended. Compared with the prior art, the method adopts manganese dioxide ore to remove Fe in the cobalt ore leaching solution 2+ Is oxidized into Fe 3+ The reaction time is greatly shortened, and the manganese dioxide ore does not belong to dangerous chemicals, so that the safety problem of operation and storage is avoided.)

1. An oxidation process of ferrous iron in cobalt ore leaching solution is characterized in that the cobalt ore leaching solution is heated to 60-70 ℃, manganese dioxide ore is added for stirring and mixing, the pH value of the solution is controlled to be less than 1.5, the oxidation reaction time is 20 min-1 h, and when the solution is in solutionFe (b) of²⁺When the content is less than 0.05g/L, the oxidation reaction is ended.

2. The process according to claim 1, wherein the amount of manganese dioxide ore added is calculated as Wherein V is the volume of the cobalt ore leaching solution,for Fe in cobalt ore leaching solution²⁺Concentration of (A), T_MnThe grade of manganese in the manganese dioxide ore.

3. The process of claim 1, wherein the manganese grade of the manganese dioxide ore is 50-70%.

4. The process according to claim 1, wherein the pH value of the solution is controlled by adding 98% concentrated sulfuric acid.

Technical Field

The invention relates to an oxidation process of ferrous iron, in particular to an oxidation process of ferrous iron in a cobalt ore leaching solution.

Background

The leaching solution of cobalt ore contains a large amount of Fe, and the Fe is mainly Fe²⁺Is present in the solution and must be oxidized to become Fe³⁺Can be easily removed from the solution by iron removal, and Fe²⁺The oxidation of (2) usually uses oxidant hydrogen peroxide or sodium chlorate, the hydrogen peroxide is injected into a reaction tank and directly mixed with the leaching solution to achieve the oxidationFe²⁺The method is carried out in an open container, and a large amount of heat is released in the reaction process, so that part of oxygen released by the decomposition of hydrogen peroxide is easily released into the air from the tank body, and Fe is not fully oxidized²⁺The utilization rate of the hydrogen peroxide is low, the hydrogen peroxide belongs to dangerous chemicals and is not easy to operate and store, and the sodium chlorate is directly put into the reaction tank to be directly mixed with the leachate so as to oxidize Fe²⁺The method has the advantages that the reaction time is long, sodium chlorate belongs to hazardous chemicals, and the sodium chlorate is easy to react with sodium pyrosulfite used for leaching cobalt ores to generate potential safety hazards and is difficult to operate and store.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a process for improving Fe by utilizing ferrous iron in manganese dioxide ore cobalt oxide solution²⁺The oxidation effect, the reaction time is shortened, and hazardous chemicals are avoided.

The invention adopts the following technical scheme: heating the cobalt ore leaching solution to 60-70 ℃, sampling and detecting Fe in the cobalt ore leaching solution²⁺In accordance with the content of Fe²⁺Calculating the addition amount of manganese dioxide ore according to the content of the cobalt ore leaching solution, adding a certain amount of manganese dioxide ore, stirring and mixing, controlling the pH value of the solution to be less than 1.5, carrying out oxidation reaction for 20 min-1 h, stirring for a period of time, sampling and detecting Fe²⁺If Fe²⁺The content of (D) is less than 0.05g/L, and the oxidation reaction is finished.

Further, the formula for calculating the adding amount of the manganese dioxide ore is Wherein V is the volume of the cobalt ore leaching solution,for Fe in cobalt ore leaching solution²⁺Concentration of (A), T_MnThe grade of manganese in the manganese dioxide ore.

Further, the manganese grade of the manganese dioxide ore is 50% -70%.

Further, the pH value of the solution is regulated by adding 98% concentrated sulfuric acid.

The cobalt ore leaching solution is obtained by performing primary leaching and secondary reduction leaching on cobalt ore.

The invention utilizes manganese dioxide and Fe in cobalt ore leaching solution²⁺The reaction is carried out under acidic conditions to oxidize ferrous iron into ferric iron, and the reaction formula is shown as formula (1):

MnO₂+4H⁺+2Fe²⁺＝2Fe³⁺+Mn²⁺+2H₂O (1)

the invention has the beneficial effects that: compared with the prior art, the invention adopts the Fe in manganese dioxide ore and cobalt ore leaching solution²⁺The reaction is fast, not only effectively oxidizes Fe²⁺The reaction time can be greatly shortened, and the manganese dioxide ore does not belong to dangerous chemicals, so that the safety problem of operation and storage is avoided.

Detailed Description

The following examples are given to further illustrate the embodiments of the present invention.

Stirring and slurrying the cobalt ore according to the ratio of water to ore to water of 1:3, heating the slurried cobalt ore, adding concentrated sulfuric acid to perform primary leaching, stirring and filtering; directly feeding the obtained acid leaching solution into a transfer tank for iron removal, performing secondary slurrying on the obtained acid leaching residue, adding sodium pyrosulfite for secondary reduction leaching, and adding manganese dioxide ore into the cobalt ore leaching solution obtained after the treatment for oxidation treatment to ensure that Fe in the leaching solution is oxidized²⁺Is oxidized into Fe³⁺The oxidation treatment process comprises the following steps: heating the cobalt ore leaching solution to 60-70 ℃, according to Fe in the cobalt ore leaching solution²⁺The manganese dioxide ore addition amount is calculated by the content of the cobalt ore leaching solution and the volume of the cobalt ore leaching solution, the pH value of the solution is controlled to be less than 1.5, the oxidation reaction time is 20 min-1 h, and after the solution is stirred for a period of time, a sample is taken to detect Fe²⁺If Fe²⁺The content of (D) is less than 0.05g/L, and the oxidation reaction is finished.

Example 1

Heating 1.6L of cobalt ore leachate to 65 ℃, sampling and detecting Fe in the cobalt ore leachate²⁺Concentration of (2)9.38g/L, manganese grade T of manganese dioxide ore_MnIs 61.4%, according to the formulaCalculating the addition amount of manganese dioxide ore to be 12.00g, adding the manganese dioxide ore into the cobalt ore leaching solution, stirring and mixing, controlling the pH value to be 1.5 in the stirring process, stirring for 1h, and detecting Fe²⁺The content of (B) is 0.001 g/L.

Example 2

Heating 1.6L of cobalt ore leachate to 60 ℃, sampling and detecting Fe in the cobalt ore leachate²⁺Concentration of (2)9.38g/L, manganese grade T of manganese dioxide ore_MnIs 50% according to the formulaCalculating the addition amount of manganese dioxide ore to be 14.74g, adding manganese dioxide ore into cobalt ore leaching solution, stirring and mixing, controlling the pH value to be 1.5 in the stirring process, stirring for 20min, and detecting Fe²⁺The content of (B) is 0.001 g/L.

Example 3

Heating 1.6L of cobalt ore leachate to 70 ℃, sampling and detecting Fe in the cobalt ore leachate²⁺Concentration of (2)9.38g/L, manganese grade T of manganese dioxide ore_MnIs 70% according to the formulaCalculating the addition amount of manganese dioxide ore to be 10.53g, adding manganese dioxide ore into cobalt ore leaching solution, stirring and mixing, controlling the pH value to be 1.0 in the stirring process, stirring for 20min, and detecting Fe²⁺The content of (B) is 0.002 g/L.

Example 4

Heating 1.6L of cobalt ore leachate to 60 ℃, sampling and detecting Fe in the cobalt ore leachate²⁺Concentration of (2)9.38g/L, manganese grade T of manganese dioxide ore_MnIs 61.4%, according to the formulaCalculating the addition amount of manganese dioxide ore to be 12.00g, adding manganese dioxide ore into cobalt ore leaching solution, stirring and mixing, controlling pH to be 0.5 in the stirring process, stirring for 20min, and detecting Fe²⁺The content of (B) is 0.002 g/L.

Comparative example 1

Heating 1.6L of cobalt ore leachate to 65 ℃, sampling and detecting Fe in the cobalt ore leachate²⁺Concentration of (2)9.38g/L, manganese grade T of manganese dioxide ore_MnIs 61.4%, according to the formulaCalculating the addition amount of manganese dioxide ore to be 12.00g, adding the manganese dioxide ore into the cobalt ore leaching solution, stirring and mixing, controlling the pH value to be 2.0 in the stirring process, stirring for 1h, and detecting Fe²⁺The content of (B) was 1.28 g/L.

The invention adopts Fe in manganese dioxide ore and cobalt ore leaching solution²⁺The reaction is fast, not only effectively oxidizes Fe²⁺The reaction time can be greatly shortened, and the manganese dioxide ore does not belong to dangerous chemicals, so that the safety problem of operation and storage is avoided.