阅读说明：本技术 一种还原浸出水钴矿的方法 (Method for reducing leached hydrocobaltite ) 是由 薛伟 郑正 李晓东 易运来 毛竞 于 2019-10-14 设计创作，主要内容包括：本发明提供了一种还原浸出水钴矿的方法,包括如下步骤：将水钴矿料与水混合,得到矿浆；向矿浆中加入硫酸,加热后加入辉铜矿料,还原反应1～4h完成浸出；其中,硫酸按照浸出终点的pH值为1.3～2的量添加；辉铜矿料按照辉铜矿与水钴矿中Co金属反应所需的1.2～2.2倍的质量添加。辉铜矿可以将水钴矿中的钴从+3价还原降低为+2价,从而被硫酸浸出；同时将辉铜矿作为水钴矿浸出的还原剂,其中的铜与水钴矿反应由+1价变位+2价,也被硫酸浸出,解决了辉铜矿冶炼难的问题；浸出过程不向浸出体系引入其他有害杂质,不产生有害气体,清洁环保。(The invention provides a method for reducing leached hydrocobalt ore, which comprises the following steps: mixing the cobalt hydrate ore material with water to obtain ore pulp; adding sulfuric acid into the ore pulp, heating, adding bright copper ore material, and carrying out reduction reaction for 1-4 h to complete leaching; wherein, the sulfuric acid is added according to the amount that the pH value of the leaching end point is 1.3-2; the chalcocite material is added according to the mass which is 1.2-2.2 times of that of the Co metal in the chalcocite and the water cobalt ore required by the reaction. The chalcocite can reduce cobalt in the cobaltite from +3 to +2, so that the cobaltite is leached by sulfuric acid; meanwhile, chalcocite is used as a reducing agent for leaching the heterogenite, wherein the copper reacts with the heterogenite from +1 valence to +2 valence and is also leached by sulfuric acid, so that the problem of difficult chalcocite smelting is solved; other harmful impurities are not introduced into the leaching system in the leaching process, harmful gas is not generated, and the method is clean and environment-friendly.)

1. A method for reducing leached hydrocobaltite is characterized by comprising the following steps:

(1) Pulping: mixing the cobalt hydrate ore material with water to obtain ore pulp;

(2) Leaching: adding sulfuric acid into the ore pulp until the pH value of the ore pulp is 1.3-2, heating, adding bright copper ore material, stirring and reacting for 1-4 h to complete leaching;

wherein the chalcocite material is added according to the mass which is 1.2-2.2 times of that of the Co metal in the chalcocite and the heterogenite required by the reaction.

2. the method for reductive leaching of hydrocobalt ore according to claim 1, wherein the particle size of the hydrocobalt ore material is less than 0.6 mm.

3. the method for reductive leaching of hydrocobaltite according to claim 1, wherein the liquid-to-solid ratio of the hydrocobaltite material to water is 2:1 to 5: 1.

4. The method for reductive leaching of heterogenite according to claim 1, wherein in step (2), sulfuric acid is added into the ore pulp and stirred, and then the mixture is heated to 50-75 ℃ and added with bright copper ore material, and the stirring reaction is carried out for 1-4 hours to complete the leaching.

5. The method for reductive leaching of hydrocobaltite according to claim 4, wherein the stirring speed is 60 to 120 r/min.

6. The method for reductive leaching of hydrocobaltite according to claim 1, wherein the concentration of sulfuric acid is 25 to 150 g/L.

7. The method for reductive leaching of hydrocobaltite according to claim 1, wherein the particle size of said bright copper ore material is less than 0.6 mm.

8. The method for reductive leaching of hydrocobalt ore according to claim 1 wherein solid-liquid separation is performed after completion of leaching in step (2) to obtain leachate containing valuable metals and leaching residue.

9. The method of reductively leaching hydrocobalt ore according to claim 8, wherein the valuable metals include metallic cobalt and metallic copper.

10. The method for reductive leaching of hydrocobalt ores as claimed in claim 1, wherein the leaching rate of cobalt is greater than 94% and the leaching rate of copper is greater than 90%.

Technical Field

The invention relates to the technical field of metallurgy, in particular to a method for reducing leached hydrocobalt ore.

background

Cobalt is an important strategic metal, is used as a key functional element of a lithium battery, is very lack of cobalt resources, mostly belongs to low-grade complex associated ores, and is recovered as a byproduct of a nickel and zinc metallurgical process for a long time. Congo (gold) cobalt is abundant in resources, and half of the total amount of cobalt production in the world comes from the country. Most of the cobaltous ores are symbiotic with copper ores, and cobalt is mainly contained in hydrocobaltic ores, cobaltosic-containing brome, copper-cobalt-manganese-oxygen combination substances, copper-cobalt-containing limonite, cobalt-containing dolomite and other minerals, wherein the cobalt in the hydrocobaltic ores exists in a trivalent cobalt form and cannot be directly leached by sulfuric acid, and a reducing agent is added for heating leaching.

At present, the reducing agents used in industrial production and experimental research are mainly sodium sulfite, sodium metabisulfite, sulfur dioxide, ferrous salt and the like. Chinese patent CN200910301216.0 discloses a method for selectively leaching out heterogenite by a full-wet method, which adopts concentrated sulfuric acid or concentrated hydrochloric acid as a leaching agent, adds iron salt as a reducing agent, and performs reduction leaching at the reaction temperature of 60-90 ℃, and the leaching agent strengthens the oxidation and iron removal of an oxidant.

Sodium sulfite, sodium metabisulfite and sulfur dioxide are used as reducing agents, harmful impurities cannot be introduced into a leaching system, but in an acid system, the sodium sulfite and the sodium metabisulfite are easy to decompose to release sulfur dioxide, the solubility of the sulfur dioxide is low, the sulfur dioxide gas is easy to release in the leaching process, the leaching operation environment is deteriorated, and the consumption and the production cost of the reducing agents are increased. For example, Chinese patent 201010582776.0 discloses selective reduction leaching of cobaltite with sulfuric acid and sodium sulfite as a reducing agent, cyclone electrodeposition of the leachate is used to extract copper and cobalt, and the cobalt-extracted solution is returned for acid leaching. The method needs to add sodium sulfite as a leaching aid, acid decomposition reaction is easy to occur in the leaching process, and sulfur dioxide gas escapes to cause environmental pollution.

How to further optimize and improve the prior reduction leaching process of the cobalt ore, realize the efficient and environment-friendly leaching of cobalt from the heterogenite, and reduce the production cost is a problem to be solved urgently in the leaching process of the heterogenite.

Disclosure of Invention

The invention provides a method for reducing and leaching out heterogenite, and aims to improve the efficiency of a cobalt leaching process, reduce the leaching cost, simplify the process and avoid generating toxic gas.

In order to achieve the purpose, the invention provides the following technical scheme:

A method for reducing leached hydrocobaltite comprises the following steps:

(1) Pulping: mixing the cobalt hydrate ore material with water to obtain ore pulp;

(2) Leaching: adding sulfuric acid into the ore pulp until the pH value of the ore pulp is 1.3-2, heating, adding bright copper ore material, stirring and reacting for 1-4 h to complete leaching;

Wherein the chalcocite material is added according to the mass which is 1.2-2.2 times of that of the Co metal in the chalcocite and the heterogenite required by the reaction.

Preferably, the particle size of the water cobalt mineral aggregate is less than 0.6 mm.

Preferably, the liquid-solid ratio of the water-cobalt mineral aggregate to the water is 2: 1-5: 1.

preferably, the sulfuric acid is added into the ore pulp in the step (2), then stirring is carried out, the mixture is heated to 50-75 ℃, and then the bright copper ore material is added, and the stirring reaction is carried out for 1-4 hours, so that the leaching is completed.

More preferably, the stirring speed is 60-120 r/min.

Preferably, the concentration of the sulfuric acid is 25-150 g/L.

Preferably, the particle size of the bright copper ore material is less than 0.6 mm.

Preferably, after completion of leaching in step (2), solid-liquid separation is performed to obtain a leachate containing valuable metals.

Preferably, the valuable metals include metallic cobalt and metallic copper.

Preferably, the leaching rate of cobalt is more than 94%, and the leaching rate of copper is more than 90%.

The scheme of the invention has the following beneficial effects:

(1) The molecular formula of the heterogenite is Co₂O₃·H₂O, wherein the cobalt has a valence of +3, needs to be reduced to a valence of +2 before being leached. The molecular formula of the chalcocite is Cu₂s, sulfurThe valence of the sulfur is-2 valence, which is a strong oxidant, the valence of the sulfur is changed into +6 valence in the leaching process, and the cobalt in the heterogenite can be reduced from +3 valence to +2 valence, so that the cobalt is leached by sulfuric acid. And the chalcocite is used as a reducing agent to leach the cobaltite, other harmful impurities are not introduced into a leaching system, and the subsequent impurity removal process of cobalt leaching is facilitated.

The valence state of copper in the chalcocite is +1, and the chalcocite can also react with the hydrocobaltite, the valence state of the copper is changed from +1 to +2, and the valence state of the cobalt is reduced from +3 to + 2. The reaction equation of the specific leaching process is as follows:

5Co₂O₃·H₂O+Cu₂S+11H₂SO₄═10CoSO₄+2CuSO₄+16H₂O

(2) The copper sulphide ore of the congo (gold) part is chalcocite, the chalcocite concentrate obtained by ore dressing has low iron and sulfur contents, is difficult to smelt by adopting the modern fire process, and generally adopts a method with more complex roasting-leaching. According to the method, chalcocite is used as a water-soluble cobalt ore leaching reducing agent, copper and water-soluble cobalt ore react with + 1-valent and + 2-valent copper ions, and the problem that chalcocite is difficult to smelt is solved.

(3) About 1.1 ton of sodium sulfite which is a conventional reducing agent is consumed every ton of cobalt metal is reduced and leached, chalcocite is used as the reducing agent, so that the consumption of the part of sodium sulfite is avoided, the economic benefit of an enterprise can be effectively improved, and meanwhile, harmful gas is not generated in the leaching process, and the method is clean and environment-friendly.

Detailed Description

In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.