CN107971123A - A kind of flotation and metallurgy method of irony coated mixed copper ore - Google Patents

Abstract

The invention discloses a method for dressing and smelting iron-wrapped mixed copper ore, which belongs to the technical field of ore dressing and metallurgy. The invention performs flotation on the iron-wrapped mixed copper ore to obtain flotation copper concentrate and flotation tailings; the flotation tailings adopts magnetic separation to obtain iron-wrapped copper-containing magnetic separation concentrate and low-grade copper-containing magnetic separation Tailings; iron-coated copper-containing magnetic separation concentrates are finely ground, and concentrated sulfuric acid is used as a leaching agent to recover copper minerals through high-temperature stirring and leaching; The tailings are mixed, and the waste heat and acid are used to further recover the copper minerals in the tailings. The present invention classifies and recycles copper minerals in ores, treats iron-wrapped mixed copper ore in a targeted manner, and extracts copper resources in low-grade copper-containing magnetic separation tailings by using waste heat and residual acid, and solves the problem of iron-wrapped mixed copper ore economically and efficiently. The technical problem that mixed copper ore is difficult to recycle has improved the comprehensive utilization rate of copper resources.

Description

A kind of beneficiation and smelting method of iron-encapsulated mixed copper ore

technical field

The invention relates to a method for dressing and smelting iron-wrapped mixed copper ore, which belongs to the technical field of ore dressing and metallurgy.

Background technique

Copper is an important non-ferrous metal, and its status in national economic construction is becoming more and more important. Copper mainly exists in the form of sulfide and oxide in nature. Common copper sulfide minerals with industrial mining value include chalcopyrite, chalcocite, bornite, copper blue, etc., and copper oxide minerals include malachite. , Azurite, Cuprite, Chrysocolla, etc. However, in the process of copper mining and processing, in addition to single copper sulfide and copper oxide ore, sulfide-oxidation mixed copper ore occupies a considerable proportion of copper ore resources. Therefore, in order to meet the needs of the national economy for copper metal, To reduce the external dependence of copper, the efficient development and utilization of mixed copper ore resources is imperative.

At present, the flotation of copper sulfide ore is relatively mature; the floatability of copper oxide minerals is worse than that of copper sulfide minerals, and sulfide flotation and direct flotation are often used for enrichment. The enrichment of copper oxide ore by sulfidation flotation is widely used in industrial production, that is, sodium sulfide or sodium hydrosulfide is used as a sulfide agent to sulfide the copper oxide minerals in the ore, and then the xanthate collector is used to sulfide the copper oxide ore. Collection; During the sulfidation process of copper oxide minerals, a certain amount of ammonium sulfate or ethylenediamine can be added to achieve enhanced sulfidation of copper oxide minerals. Direct flotation is to use fatty acid or hydroxamic acid as a collector to directly float copper oxide minerals in ores, but this method is limited to copper oxide ores with relatively simple gangue minerals in ores. In addition, techniques such as segregation-flotation, acid leaching, ammonia leaching, and bacterial leaching are commonly used to treat copper oxide ore.

For sulfide-oxidation mixed copper ore, the flotation method can only recover copper sulfide minerals and partial copper oxide minerals; by leaching, although the copper oxide minerals in the ore are well recovered, the copper sulfide minerals Difficult to recycle, when the content of carbonate gangue minerals in the ore is high, the cost of direct acid leaching is high; at present, the combined dressing and smelting process is an effective method for processing mixed copper ore, which has certain flexibility and can handle different types of ore. The invention patent with application number 200510010932.5 proposes a method for extracting copper from low-grade high-calcium magnesium copper oxide ore raw ore. The method first dissolves the copper oxide minerals in the ore by normal temperature and pressure ammonia leaching technology, and leaches the tailings The flotation method is used to recover the copper sulfide minerals, and the comprehensive recovery of high-calcium-magnesium-oxygen-sulfur mixed copper ores is realized. The invention patent with the application number 201010178875.2 proposes a method for beneficiation and smelting of high binding rate carbonate gangue-type oxygen-sulfur mixed copper ore. The method first recovers high binding rate carbonate gangue-type oxygen-sulfur mixed copper ore through flotation. Copper sulfide minerals and free copper oxide minerals in copper ore, the calcium magnesium carbonate minerals in the flotation tailings are reverse flotation with fatty acids, and the medium ore containing low calcium magnesium carbonate minerals and bound copper is obtained. Sulfuric acid is added to stir and leach bound copper, and the copper-containing solution after solid-liquid separation is used to obtain copper products through metallurgical methods. The invention patent with application number 201310615690.7 is aimed at low-grade mixed copper ore. Firstly, a new type of high-efficiency collector MA is selected as the collector for copper sulfide ore to directly float copper sulfide ore, and then copper oxide is recovered through sulfide flotation and direct flotation respectively. For the ore, the new high-efficiency collector MA was selected as the sulfide flotation collector, and sodium oleate was used as the direct flotation collector for copper oxide ore. The flotation mixed concentrate was concentrated for acid leaching treatment, and the filtrate was collected after filtration.

In summary, oxygen-sulfur mixed copper ore can achieve comprehensive recovery of copper resources in the ore through ore dressing, leaching, dressing and smelting, etc. These ores can be dissociated from the copper minerals by conventional crushing and grinding. It is beneficial for subsequent technology to recycle it. However, in copper ore resources, some copper oxide ores are closely symbiotic with iron minerals. The copper oxide minerals in the ore are wrapped by hematite and limonite, and it is difficult to recover them by conventional dressing and smelting methods. The invention patent with the application number 201710139088.9 proposes a method for recycling wrapped copper oxide ore, which is difficult to recover by flotation and has a low direct acid leaching rate. The method adopts vulcanization, xanthate, Fatty acid salt and hydroxamic acid are combined to flotation free copper oxide, and magnetic separation recovers iron and biotite minerals wrapped in copper minerals in the ore, and a large number of low-grade copper-containing tailings are separated. Coarse concentrate containing wrapped copper is leached under high temperature and pressure to strengthen the recovery of copper ore resources. The high-temperature leached slurry is mixed with low-grade copper-containing tailings to continue leaching the copper minerals in the tailings with waste heat and acid, so that the copper minerals in the tailings cannot be directly The coated copper oxide ore recovered by flotation and direct acid leaching can be efficiently recycled. The invention patent with the application number of 201710139134.5 proposes a method for the combined recycling and utilization of copper oxide ore with solid inclusions. It adopts strong magnetic separation to obtain the magnetic products wrapped in copper oxide, filters the magnetic products, uses microwave drying and heating, and utilizes The selectivity of microwave heating to different minerals in solid inclusions makes the minerals have different temperature rises and volume expansions to produce cracks, which provides diffusion channels for the subsequent sulfuric acid leaching, improves the leaching rate and leaching rate, and efficiently recovers this refractory copper. mine resources. However, these two methods use high-temperature pressure-stirring leaching and microwave drying and heating technology to treat the copper-containing inclusions in the ore. Although the copper leaching rate can be improved, the high-temperature pressure stirring leaching equipment used and microwave drying and The cost of heating equipment is high, and the operation and maintenance requirements are high, and this method is mainly aimed at the recovery of copper oxide ore.

Contents of the invention

Aiming at the deficiencies of the prior art, the present invention provides a dressing and smelting method of iron-encased mixed copper ore, that is, performing flotation on iron-encased mixed copper ore to obtain flotation copper concentrate and flotation tailings; flotation tailings The ore adopts magnetic separation to obtain iron-coated copper-containing magnetic separation concentrate and low-grade copper-containing magnetic separation tailings; after the iron-coated copper-containing magnetic separation concentrate is finely ground, concentrated sulfuric acid is used as the leaching agent, and the high-temperature Stirring leaching recovers the copper minerals; the high-temperature slurry after magnetic separation concentrate leaching is mixed with copper-containing magnetic separation tailings, and the waste heat and acid are used to further recover copper minerals in the tailings, so that direct flotation recovery is not possible. The iron-coated mixed copper ore extracted by acid leaching can be efficiently recycled.

A method for dressing and smelting iron-encapsulated mixed copper ore is characterized in that the specific steps are as follows:

(1) Crush and grind the iron-encapsulated mixed copper ore to a mass percentage of -74μm, which accounts for 70-80% of the mass percentage, and adjust the slurry until the mass percentage concentration of the ore pulp is 30-40%. For packaged mixed copper ore, add 400~800g vulcanizing agent, 300~600g collector, and 30~100g foaming agent in sequence, and perform a roughing operation to obtain a roughing concentrate and a roughing tailings. For the iron-coated mixed copper ore, add 100~200g vulcanizing agent, 75~150g collector and 15~50g foaming agent to the tailings of the primary roughing in order to carry out the secondary roughing operation to obtain the secondary roughing concentrate and secondary rougher tailings (secondary rougher tailings are flotation tailings), the first rougher concentrate and the second rougher concentrate are combined for concentration operations to obtain flotation copper concentrate and concentrated tailings ore, and the selected tailings return to the slurry for a roughing operation;

(2) Under the condition of a magnetic field strength of 0.8~1.4T, the secondary roughing tailings obtained in step (1) are subjected to magnetic separation to obtain iron-coated copper-containing magnetic separation concentrates and low-grade copper-containing magnetic separation tailings ;

(3) According to the step (2), the mass percentage of the finely ground copper-containing magnetic separation concentrate to -45 μm particle size is greater than 85%, and the liquid-solid mass ratio of the pulp is (2~3):1. Under the condition of stirring at a temperature of 75-90°C, add concentrated sulfuric acid to obtain a pulp mixture A and leaching for 120-180 minutes to obtain a leached pulp;

(4) Add the magnetic separation tailings obtained in step (2) to the leaching pulp obtained in step (3) and mix evenly to obtain the pulp mixture B, and continue leaching for 180~240min under stirring conditions, and separate the solid and liquid to obtain the copper-containing leachate and leaching tailings slag;

In the step (1), the mass percentage of copper in the iron-wrapped mixed copper ore is 1.0-1.8%, and the oxidation rate of copper is not less than 70%; the copper content in the iron-wrapped mixed copper ore is 100% Calculated, the content of copper in iron minerals is 35~45%, and the iron minerals are hematite and/or limonite; the vulcanizing agent is sodium sulfide, the collector is butyl xanthate, and the foaming agent is 2 No. oil;

The concentration of sulfuric acid in the step (3) pulp mixture A is 35 ~ 80g/L;

The liquid-solid mass ratio in the pulp mixture B in the step (4) is (2~3):1;

The leaching process of the step (4) utilizes the residual heat and residual acid leached in the step (3), without additional heating and without adding new concentrated sulfuric acid.

Beneficial effects of the present invention:

(1) In the present invention, the copper sulfide minerals in the iron-encapsulated mixed copper ore are first flotation-separated, which not only obtains qualified flotation copper concentrates, but also reduces the difficulty of leaching copper sulfide minerals in the subsequent leaching process ;

(2) The present invention uses strong magnetic separation to enrich the copper minerals wrapped in hematite and/or limonite in the flotation tailings, which are difficult to recover by flotation, and provide the targeted leaching of iron-wrapped copper ores. Raw materials; at the same time, a large number of low-grade copper-containing magnetic separation tailings are separated by strong magnetic separation, which can greatly reduce the amount of ore in the high-temperature stirring leaching process and reduce the cost of leaching;

(3) The present invention uses fine grinding to further dissociate the copper minerals in the copper-containing magnetic separation concentrate wrapped in iron, which can increase the leaching speed and leaching rate of copper minerals in the magnetic separation concentrate; The final high-temperature slurry is mixed with copper-containing magnetic separation tailings, and the copper minerals lost in the tailings are further recovered by using waste heat and waste acid to improve the recovery rate of copper;

(4) The present invention classifies and recovers copper minerals in ores, specifically treats iron-wrapped mixed copper ores, and utilizes waste heat and waste acid to leach copper resources in low-grade copper-containing magnetic separation tailings, which can be solved economically and efficiently. The technical problem that iron-coated mixed copper ore is difficult to recycle can improve the comprehensive utilization rate of copper resources.

Description of drawings

Fig. 1 is a process flow diagram of the present invention.

Detailed ways

The present invention will be described in further detail below in conjunction with specific examples, but the protection scope of the present invention is not limited to the content described.

Embodiment 1: the mass percent composition of copper in the irony wrapped copper ore of the present embodiment is 1.0%, and the oxidation rate of copper is 70%; Taking the copper content in the iron wrapped copper mixed ore as 100%, The content of copper in iron minerals is 35%, and the iron minerals are hematite and limonite;

As shown in Figure 1, a kind of dressing and smelting method of iron-encapsulated mixed copper ore, concrete steps are as follows:

(1) Crush and grind the iron-coated mixed copper ore until the mass percentage of -74μm grain size accounts for 70%. In the mine plan, add 400g of vulcanizing agent (the vulcanizing agent is sodium sulfide), 300g of collector (the collector is butyl xanthate) and 30g of foaming agent (the foaming agent is No. 2 oil) in sequence to carry out a roughing operation To obtain the first roughing concentrate and the first roughing tailings, based on per ton of iron-encapsulated mixed copper ore, add 100g of vulcanizing agent, 75g collector and 15g foaming agent to the first roughing tailings for the second The roughing operation obtains the secondary roughing concentrate and the secondary roughing tailings, and the primary roughing concentrate and the secondary roughing concentrate are combined for the beneficiation operation to obtain the flotation copper concentrate and the beneficiation tailings, and the beneficiation The tailings return to pulping for a roughing operation;

(2) Under the condition of a magnetic field strength of 0.8T, magnetically separate the secondary roughing tailings obtained in step (1) to obtain iron-encased copper-containing magnetic separation concentrates and low-grade copper-containing magnetic separation tailings;

(3) According to the step (2), the copper-containing magnetic separation concentrate obtained by fine grinding to -45μm particle size is 85% by mass, and the liquid-solid mass ratio of the pulp is 2:1, and the temperature is 75°C Under the stirring condition of the mixture, concentrated sulfuric acid was added to obtain the pulp mixture A and the leaching reaction was carried out for 120 minutes to obtain the leached pulp, wherein the concentration of sulfuric acid in the pulp mixture A was 35g/L;

(4) Add the magnetic separation tailings obtained in step (2) to the leaching pulp obtained in step (3) and mix uniformly to obtain a pulp mixture B, continue leaching for 180 minutes under stirring conditions, and separate solid and liquid to obtain copper-containing leachate and leaching tailings. Wherein the liquid-solid mass ratio in the slurry mixture B is 2:1;

The comprehensive recovery rate of copper in the present embodiment is 90.2%.

Embodiment 2: the mass percent content of copper in the irony wrapped copper ore of the present embodiment is 1.4%, and the oxidation rate of copper is 79.2%; Taking the copper content in the iron wrapped mixed copper ore as 100%, The content of copper in iron minerals is 39.5%, and the iron minerals are hematite and limonite;

As shown in Figure 1, a kind of dressing and smelting method of iron-encapsulated mixed copper ore, concrete steps are as follows:

(1) Crush and grind the iron-coated mixed copper ore to a mass percentage of -74μm, which accounts for 75% of the mass percentage, and adjust the slurry to a mass percentage concentration of 35%. In the mine plan, add 550g of vulcanizing agent (the vulcanizing agent is sodium sulfide), 500g of collector (the collector is butyl xanthate) and 75g of foaming agent (the foaming agent is No. 2 oil) in order to carry out a roughing operation To obtain the first roughing concentrate and the first roughing tailings, based on per ton of iron-coated mixed copper ore, add 137.5g sulfiding agent, 125g collector and 37.5g foaming agent to the first roughing tailings successively The secondary roughing operation obtains the secondary roughing concentrate and the secondary roughing tailings, and the primary roughing concentrate and the secondary roughing concentrate are combined for the beneficiation operation to obtain the flotation copper concentrate and the concentrated tailings, The selected tailings are returned to the slurry for a roughing operation;

(2) Under the condition of a magnetic field strength of 1.2T, magnetically separate the secondary roughing tailings obtained in step (1) to obtain iron-encased copper-containing magnetic separation concentrates and low-grade copper-containing magnetic separation tailings;

(3) According to the step (2), the mass percentage of the finely ground copper-containing magnetic separation concentrate to -45μm particle size is 88%. Under the agitation condition of above, add concentrated sulfuric acid to obtain pulp mixture A and leaching reaction for 150min to obtain leached pulp, wherein the concentration of sulfuric acid in pulp mixture A is 60g/L;

(4) Add the magnetic separation tailings obtained in step (2) to the leaching pulp obtained in step (3) and mix evenly to obtain a pulp mixture B, continue leaching for 210 minutes under stirring conditions, and separate solid and liquid to obtain copper-containing leachate and leaching tailings. Wherein the liquid-solid mass ratio in the slurry mixture B is 2.5:1;

The comprehensive recovery rate of copper in the present embodiment is 88.7%.

Embodiment 3: the mass percent composition of copper in the irony wrapped copper ore of the present embodiment is 1.8%, and the oxidation rate of copper is 87%; Taking the copper content in the iron wrapped copper mixed ore as 100%, The content of copper in iron minerals is 45%, and the iron minerals are hematite and limonite;

As shown in Figure 1, a kind of dressing and smelting method of iron-encapsulated mixed copper ore, concrete steps are as follows:

(1) Crush and grind the iron-coated mixed copper ore until the mass percentage of -74μm grain size accounts for 80%, and adjust the slurry to a mass percentage concentration of 40%, and the iron-coated mixed copper ore per ton In the mine plan, add 800g vulcanizing agent (the vulcanizing agent is sodium sulfide), 600g collector (the collector is butyl xanthate) and 100g foaming agent (the foaming agent is No. 2 oil) in sequence, and carry out a roughing operation To obtain the first roughing concentrate and the first roughing tailings, based on per ton of iron-coated mixed copper ore, add 200g sulfiding agent, 150g collector and 50g foaming agent to the first roughing tailings for the second The roughing operation obtains the secondary roughing concentrate and the secondary roughing tailings, and the primary roughing concentrate and the secondary roughing concentrate are combined for the beneficiation operation to obtain the flotation copper concentrate and the beneficiation tailings, and the beneficiation The tailings return to pulping for a roughing operation;

(2) Under the condition of a magnetic field strength of 1.4T, magnetically separate the secondary roughing tailings obtained in step (1) to obtain iron-encased copper-containing magnetic separation concentrates and low-grade copper-containing magnetic separation tailings;

(3) According to the step (2), the copper-containing magnetic separation concentrate obtained by finely grinding to -45μm particle size is 90% by mass, and the liquid-solid mass ratio of the slurry is 3:1, and the temperature is 90°C Under the stirring condition of the mixture, add concentrated sulfuric acid to obtain pulp mixture A and leaching reaction for 180min to obtain leached pulp, wherein the concentration of sulfuric acid in pulp mixture A is 80g/L;

(4) Add the magnetic separation tailings obtained in step (2) to the leaching pulp obtained in step (3) and mix uniformly to obtain a pulp mixture B, continue leaching for 240 minutes under stirring conditions, and separate solid and liquid to obtain copper-containing leachate and leaching tailings. Wherein the liquid-solid mass ratio in the slurry mixture B is 3:1;

The comprehensive recovery rate of copper in the present embodiment is 86.5%.

Claims (4)

1. a method for dressing and smelting of iron-encapsulated mixed copper ore is characterized in that, the concrete steps are as follows: (1) Crush and grind the iron-encapsulated mixed copper ore to a mass percentage of -74μm, which accounts for 70-80% of the mass percentage, and adjust the slurry until the mass percentage concentration of the ore pulp is 30-40%. For packaged mixed copper ore, add 400~800g vulcanizing agent, 300~600g collector, and 30~100g foaming agent in sequence, and perform a roughing operation to obtain a roughing concentrate and a roughing tailings. For the iron-coated mixed copper ore, add 100~200g vulcanizing agent, 75~150g collector and 15~50g foaming agent to the tailings of the primary roughing in order to carry out the secondary roughing operation to obtain the secondary roughing concentrate and secondary roughing tailings, the first roughing concentrate and the second roughing concentrate are combined for beneficiation operation to obtain flotation copper concentrate and concentrated tailings, and the selected tailings are returned to slurry for a roughing operation ; (2) Under the condition of a magnetic field strength of 0.8~1.4T, the secondary roughing tailings obtained in step (1) are subjected to magnetic separation to obtain iron-coated copper-containing magnetic separation concentrates and low-grade copper-containing magnetic separation tailings ; (3) According to the step (2), the mass percentage of the finely ground copper-containing magnetic separation concentrate to -45 μm particle size is greater than 85%, and the liquid-solid mass ratio of the pulp is (2~3):1. Under the condition of stirring at a temperature of 75-90°C, add concentrated sulfuric acid to obtain a pulp mixture A and leaching for 120-180 minutes to obtain a leached pulp; (4) Add the magnetic separation tailings obtained in step (2) to the leaching pulp obtained in step (3) and mix evenly to obtain the pulp mixture B, and continue leaching for 180~240min under stirring conditions, and separate the solid and liquid to obtain the copper-containing leachate and leaching tailings scum. 2. The dressing and smelting method of iron-encapsulated mixed copper ore according to claim 1, characterized in that: step (1) the mass percentage of copper in the iron-enclosed mixed copper ore is 1.0-1.8%, and the oxidation of copper The copper content in the iron minerals is 35-45% based on the copper content in the iron-coated mixed copper ore as 100%, and the iron minerals are hematite and/or limonite Mine; the vulcanizing agent is sodium sulfide, the collector is butyl xanthate, and the foaming agent is No. 2 oil. 3. The dressing and smelting method of iron-encapsulated mixed copper ore according to claim 1, characterized in that: the concentration of sulfuric acid in the slurry mixture A in step (3) is 35-80 g/L. 4. The method for dressing and smelting iron-encapsulated mixed copper ore according to claim 1, characterized in that the liquid-solid mass ratio in the slurry mixture B in step (4) is (2~3):1.