阅读说明：本技术 一种从硫化矿石中浸出铜、金和银的方法 (Method for leaching copper, gold and silver from sulfide ore ) 是由 董飘平 蒋航宇 王璐 刘宇豪 赵尹 于 2021-08-10 设计创作，主要内容包括：本发明公开了一种从硫化矿石中浸出铜、金和银的方法,a)将硫化矿原料研磨得到粒径为45-106μm的浸出原料；b)将所述浸出原料与离子液体混合,得混合溶液；c)在所述混合溶液中加入一定量的氧化剂和络合剂在浸出槽中反应；浸铜时添加过量的所述氧化剂,不添加所述络合剂；浸金、银时所述氧化剂添加量为0.1-5.0g/kg,所述络合剂的添加量为1.0-50.0g/kg；d)一定时间后结束反应得浸出液,对所述浸出液进行过滤,固液分离得到滤渣和滤液。本发明采用上述结构的一种从硫化矿石中浸出铜、金和银的方法,整个工艺过程不需要高温高压的操作条件具有流程操作简单、设备投资低、运行成本低、环保无污染等优点。(The invention discloses a method for leaching copper, gold and silver from sulfide ore, a) grinding sulfide ore raw materials to obtain leaching raw materials with the grain diameter of 45-106 mu m; b) mixing the leaching raw material with ionic liquid to obtain a mixed solution; c) adding a certain amount of oxidant and complexing agent into the mixed solution to react in a leaching tank; adding excessive oxidant during copper leaching, and not adding the complexing agent; the addition amount of the oxidant is 0.1-5.0g/kg during gold and silver leaching, and the addition amount of the complexing agent is 1.0-50.0 g/kg; d) and finishing the reaction after a certain time to obtain a leaching solution, filtering the leaching solution, and carrying out solid-liquid separation to obtain filter residues and a filtrate. The method for leaching copper, gold and silver from sulfide ore with the structure does not need high-temperature and high-pressure operation conditions in the whole process, and has the advantages of simple process operation, low equipment investment, low operation cost, environmental protection, no pollution and the like.)

1. A method of leaching copper, gold and silver from sulphide ores, characterised in that: the method comprises the following steps: a) grinding the sulfide ore raw material to obtain a leaching raw material with the particle size of 45-106 microns;

b) mixing the leaching raw material with ionic liquid to obtain a mixed solution;

c) adding a certain amount of oxidant and complexing agent into the mixed solution to react in a leaching tank; adding excessive oxidant during copper leaching, and not adding the complexing agent; the addition amount of the oxidant is 0.1-5.0g/kg during gold and silver leaching, and the addition amount of the complexing agent is 1.0-50.0 g/kg;

d) and finishing the reaction after a certain time to obtain a leaching solution, filtering the leaching solution, and carrying out solid-liquid separation to obtain filter residues and a filtrate.

2. A method of leaching copper, gold and silver from sulphide ores as claimed in claim 1, in which: in the step b), the ionic liquid is composed of one or a mixture of more of 1-butyl-3-methylimidazolium hydrogen sulfate, 1-pentyl-3-methylimidazolium hydrogen sulfate, 1-hexyl-3-methylimidazolium hydrogen sulfate, 1-heptyl-3-methylimidazolium hydrogen sulfate and 1-octyl-3-methylimidazolium hydrogen sulfate.

3. A method of leaching copper, gold and silver from sulphide ores as claimed in claim 1, in which: in the step b), the liquid-solid ratio (mL/g) of the ionic liquid to the leaching raw material is 10-100: 1.

4. A method of leaching copper, gold and silver from sulphide ores as claimed in claim 1, in which: in the step c), the oxidant is ferric sulfate, and the complexing agent is thiourea.

5. A method of leaching copper, gold and silver from sulphide ores as claimed in claim 1, in which: in the step c), the leaching temperature in the leaching tank is 20-80 ℃, the stirring speed is 50-1000rpm, and the leaching time is 24-50 h.

6. A method of leaching copper, gold and silver from sulphide ores as claimed in claim 1, in which: in the step d), the pH value of the leachate is less than 2.

7. A method of leaching copper, gold and silver from sulphide ores as claimed in claim 1, in which: in the step d), the equipment adopted for solid-liquid separation is a 0.45 mu m cellulose acetate filter.

8. A method of leaching copper, gold and silver from sulphide ores as claimed in claim 1, in which: in the step d), the filter residue is one or more of copper, gold and silver.

Technical Field

The invention relates to the technical field of hydrometallurgy, in particular to a method for leaching copper, gold and silver from sulfide ores.

Background

Chalcopyrite is a copper-iron sulfide mineral, and the wet leaching method of the chalcopyrite mainly focuses on the directions of bioleaching, normal-pressure chlorine salt leaching, ammonia leaching, pressure acid leaching and the like. Biological metallurgy is a new technology which is intersected with microbiology and hydrometallurgy, but the application of the biological metallurgy is influenced by the properties of ores, geographical conditions and regional environments, and the biological metallurgy is difficult to be applied to the large scale of industry. Aiming at the characteristics of poor chalcopyrite bioleaching effect and long leaching period, the chalcopyrite bioleaching still has a long way. The leaching process of normal-pressure chlorine salt leaching is complex, the equipment is seriously corroded, and the cycle of leaching the chalcopyrite is long, so that the development and application of the chalcopyrite are restricted. Although ammonia leaching has the advantage of being operated under non-corrosive conditions, the ammonia leaching has the defects of large equipment investment and unsuitability for large-scale batch production due to oxygen consumption in the leaching process, and the application is not wide.

The most widely applied is pressure leaching at present, and the pressure leaching technology of the chalcopyrite is divided into three types, one is low-temperature leaching at the temperature of 110-115 ℃, and sulfur in copper sulfide ore is converted into elemental sulfur; the second is moderate temperature leaching at 130-150 ℃, which improves chalcopyrite dissolution by increasing temperature and adding some chloride; the third is high temperature leaching at 200-220 c, where chalcopyrite leaching is rapid, sulphide minerals are fully oxidised by oxygen at high pressure and the copper is leached into solution as copper sulphate. However, the high-pressure leaching has the defects of large equipment investment, high equipment corrosion resistance requirement and the like. The wet leaching of gold and silver is usually carried out by cyanidation leaching, and although the cyanidation leaching technology is mature, the leaching agent cyanide has the defects of high toxicity, low leaching speed and the like. Therefore, the development of a new, green, environmentally friendly and sustainable sulfide leaching method is urgent.

Disclosure of Invention

The invention aims to provide a method for leaching copper, gold and silver from sulfide ores, which does not need high-temperature and high-pressure operation conditions in the whole process, has the advantages of simple process operation, low equipment investment, low operation cost, environmental protection, no pollution and the like, solves the defects that the traditional sulfide needs high-temperature and high-pressure leaching, the equipment has high pressure resistance level, the corrosion resistance requirement is high, the equipment investment is large and the like, and provides a new method for leaching the sulfide.

In order to achieve the above object, the present invention provides a method for leaching copper, gold and silver from a sulfide ore, comprising the steps of:

a) grinding the sulfide ore raw material to obtain a leaching raw material with the particle size of 45-106 microns;

b) mixing the leaching raw material with ionic liquid to obtain a mixed solution;

c) adding a certain amount of oxidant and complexing agent into the mixed solution to react in a leaching tank; adding excessive oxidant during copper leaching, and not adding the complexing agent; the addition amount of the oxidant is 0.1-5.0g/kg during gold and silver leaching, and the addition amount of the complexing agent is 1.0-50.0 g/kg;

d) and finishing the reaction after a certain time to obtain a leaching solution, filtering the leaching solution, and carrying out solid-liquid separation to obtain filter residues and a filtrate.

Preferably, in step b), the ionic liquid is one or more of 1-butyl-3-methylimidazolium hydrogen sulfate, 1-pentyl-3-methylimidazolium hydrogen sulfate, 1-hexyl-3-methylimidazolium hydrogen sulfate, 1-heptyl-3-methylimidazolium hydrogen sulfate and 1-octyl-3-methylimidazolium hydrogen sulfate.

Preferably, in the step b), the liquid-solid ratio (mL/g) of the ionic liquid to the leaching raw material is 10-100: 1.

Preferably, in step c), the oxidizing agent is ferric sulfate, and the complexing agent is thiourea.

Preferably, in the step c), the leaching temperature in the leaching tank is 20-80 ℃, the stirring speed is 50-1000rpm, and the leaching time is 24-50 h.

Preferably, in step d), the pH of the leachate is less than 2.

Preferably, in step d), the solid-liquid separation equipment is a 0.45 μm cellulose acetate filter.

Preferably, in step d), the filter residue is one or more of copper, gold and silver.

The invention has the beneficial effects that:

(1) the organic solvent in the used leaching agent is a green solvent, is environment-friendly and has no pollution;

(2) copper, gold and silver in the sulfide ore can be effectively leached under the conditions of normal temperature and normal pressure; under the same conditions, the leaching rates of copper, gold and silver are far better than those of sulfuric acid;

(3) the whole process does not need high-temperature and high-pressure operation conditions, and has the advantages of simple process operation, low equipment investment, low operation cost, environmental protection, no pollution and the like.

The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.

Drawings

FIG. 1 is a process flow diagram of a method of leaching copper, gold and silver from a sulfide ore according to the present invention.

Detailed Description

The present invention will be further described with reference to examples, in which various chemicals and reagents are commercially available unless otherwise specified.

Example 1

10.0g of dried chalcopyrite (wherein Cu is 20.31%, Fe is 34.06%, Zn is 4.46%, Si is 0.23%, Co is 0.1%, Ca is 0.08%) is ground to 45-106 μm, mixed with 1.0L 20% of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid at 70 ℃, added with 40.0g of ferric sulfate and heated and stirred for reaction in a water bath kettle, wherein the stirring speed is 500rpm, and the leaching time is 24 h. After the experiment, the copper-containing filtrate and the filter residue are obtained by filtering the mixture by using a 0.45 mu m cellulose acetate filter. The leaching rate of copper by sampling, detecting and analyzing is 65.4%.

Example 2

10.0g of dried chalcopyrite (wherein Cu is 20.31%, Fe is 34.06%, Zn is 4.46%, Si is 0.23%, Co is 0.1%, Ca is 0.08%) is ground to 45-106 μm, mixed with 1.0L of 20% 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid at 60 ℃, added with 40.0g of ferric sulfate and heated and stirred in a water bath kettle for reaction, wherein the stirring speed is 500rpm, and the leaching time is 24 h. After the experiment, the copper-containing filtrate and the filter residue are obtained by filtering the mixture by using a 0.45 mu m cellulose acetate filter. The leaching rate of copper by sampling detection and analysis is 61.2%.

Example 3

10.0g of dried chalcopyrite (wherein Cu is 20.31%, Fe is 34.06%, Zn is 4.46%, Si is 0.23%, Co is 0.1%, Ca is 0.08%) is ground to 45-106 μm, and the mixture is respectively mixed with 1.0L of 10%, 50%, 100% of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid and 1mol/L of sulfuric acid at 70 ℃, 40.0g of ferric sulfate is added to be heated and stirred in a water bath kettle for reaction, wherein the stirring speed is 500rpm, and the leaching time is 24 h. After the experiment, the copper-containing filtrate and the filter residue are obtained by filtering the mixture by using a 0.45 mu m cellulose acetate filter. 10%, 50% and 100% of the leaching rates of copper corresponding to the 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid and 1mol/L of sulfuric acid are respectively 55.1%, 82.2%, 86.6% and 23.2%.

Example 4

25.0g of dried sulfide ore (wherein Au is 5.65g/t, Ag is 18.72g/t, Cu is 1.52%, Pb is 0.36%, Zn is 0.08%, and Fe is 9.22%) is ground to 45-106 μm, mixed with 100mL of 20% of 1-butyl-3-methylimidazole hydrogen sulfate ionic liquid at 50 ℃, and added with 12.5mg of ferric sulfate and 0.5g of thiourea to be heated and stirred in a water bath for reaction, wherein the stirring speed is 500rpm, and the leaching time is 50 h. After the experiment is finished, filtering the mixture by using a 0.45 mu m cellulose acetate filter to obtain filtrate and filter residue containing the gold and the silver. The leaching rates of gold and silver analyzed by sampling detection are 85.1% and 60.3% respectively.

Example 5

25.0g of dried sulfide ore (wherein Au is 5.65g/t, Ag is 18.72g/t, Cu is 1.52%, Pb is 0.36%, Zn is 0.08%, Fe is 9.22%) is ground to 45-106 μm, and the ground sulfide ore is mixed with 100mL of 20% of 1-butyl-3-methylimidazolium hydrogen sulfate, 1-pentyl-3-methylimidazolium hydrogen sulfate, 1-hexyl-3-methylimidazolium hydrogen sulfate, 1-heptyl-3-methylimidazolium hydrogen sulfate and 1-octyl-3-methylimidazolium hydrogen sulfate ionic liquid at 50 ℃, 12.5mg of ferric sulfate and 0.5g of thiourea are added into the mixture, and the mixture is heated and stirred to react in a water bath kettle, wherein the stirring speed is 500rpm, and the leaching time is 50 h. After the experiment is finished, filtering the mixture by using a 0.45 mu m cellulose acetate filter to obtain filtrate and filter residue containing the gold and the silver. The leaching rates of gold and silver are respectively 85.1%, 72.3%, 60.8%, 41.4% and 26.6%, and 60.3%, 43.7%, 36.7%, 25.2% and 14.9%.

Example 6

25.0g of dried sulfide ore (wherein Au is 5.65g/t, Ag is 18.72g/t, Cu is 1.52%, Pb is 0.36%, Zn is 0.08%, Fe is 9.22%) is ground to 45-106 μm, and the ground sulfide ore is mixed with 100mL of 20% of ionic liquid of different anions (Cl, BF4, CH3SO3 and N (CN)2) based on 1-butyl-3-methylimidazole cation at 50 ℃, 12.5mg of ferric sulfate and 0.5g of thiourea are added to be heated and stirred in a water bath kettle, wherein the stirring speed is 500rpm, and the leaching time is 50 h. After the experiment is finished, filtering the mixture by using a 0.45 mu m cellulose acetate filter to obtain filtrate containing gold and silver and filter residue. The leaching rates of the silver are respectively 7.8%, 28.8%, 56.1% and 1.2% by sampling detection analysis.

Comparative analytical examples 1 to 6

The results of examples 1-2 show that the higher the temperature, the higher the leaching rate of copper.

The results of example 3 show that the leaching rate of copper increases with increasing concentration of ionic liquid and is much higher than that of sulfuric acid under the same conditions.

The results of examples 4-5 show that a series of (n-alkyl) methylimidazole HSO ionic liquids were investigated to show that the extraction of gold and silver decreased with increasing chain length, partly because the viscosity of the ionic liquid increased with increasing chain length.

The results of example 6 show that the extraction rate of silver by ionic liquids of different anions (CI, BF4, CHSO, NCN) is lower than that of (HSO) ionic liquids based on 1-butyl-3-methylimidazole cation.

Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.