Efficient flotation separation method for complex copper-iron sulfide ore

Abstract

The invention relates to an efficient flotation separation method for complex copper-iron sulfide ore, and belongs to the technical field of flotation reagents. A combined collecting agent is prepared, the combined collecting agent is composed of 75-80 parts of amino trimethylene phosphonic acid, 10-15 parts of xanthate, 5-10 parts of ethionine ester and 0.5-1 part of polyol fatty acid ester, and the mass concentration of the combined collecting agent is 30%-50%; pulping: adding 200-800g / t of vulcanizing agent into the complex copper-iron sulfide ore, grinding the complex copper-iron sulfide ore until the complex copper-iron sulfide ore with the fineness of-0.074 mm accounts for 65-90%, and then pulping the complex copper-iron sulfide ore until ore pulp with the solid concentration of 25-40wt% is obtained; and flotation is conducted, specifically, the ore pulp with the solid concentration being 25-40 wt% is subjected to flotation operation of one-time roughing, three to four times of concentration and two to three times of sweeping, copper concentrate and sulfur tailings are obtained, and the flotation process is conducted through a combined collecting agent in the flotation operation process of one-time roughing, three to four times of concentration and two to three times of sweeping. The novel combined collecting agent is developed to serve as a flotation reagent for efficient separation of chalcopyrite and pyrite, and an excellent complex copper-iron sulfide mineral flotation separation effect is achieved in ore pulp under the low-alkali condition.

Description

Technical Field

[0001] The invention relates to a high-efficiency flotation separation method for complex copper-iron sulfide ore, belonging to the technical field of flotation reagents. Background Art

[0002] As one of the longest-used metals in human history, copper metal plays a vital role in production activities. In the ore dressing stage, chalcopyrite is the main target mineral, and it is also associated with iron sulfide minerals. In industrial applications, flotation technology is mainly used to selectively flotate and recover chalcopyrite. Given that chalcopyrite and pyrite have similar surface physical and chemical properties, they both have good floatability in the flotation slurry environment, which makes it difficult to separate chalcopyrite from pyrite by flotation. Therefore, achieving selective separation of the two minerals is of great significance to the efficient utilization of copper resources.

[0003] There are two main types of flotation separation for copper-sulfur ores: copper-preferential flotation process and copper-sulfur mixed flotation-copper-sulfur mixed concentrate regrinding and re-separation beneficiation process.

[0004] In industry, copper-sulfur separation mainly uses xanthate as a collector and lime as a pH adjuster and inhibitor to adjust the pulp pH to high alkalinity to inhibit pyrite and pyrrhotite. In the traditional copper-sulfur separation process under high alkaline environment, the amount of lime used is generally 5-15kg / t, and the pulp pH is >12. The use of such a large amount of lime will inevitably lead to serious scaling of equipment and pipelines, reduce the service life of the equipment, and is not conducive to long-term actual production. For the xanthate system, even if a low-carbon chain ethyl xanthate is used as a collector, it still has a certain collection ability for pyrite in a low-alkali environment. In recent years, ester collectors such as ethylthiocarbamate have also been gradually used in the flotation of copper-iron sulfide ores. Although ester collectors have good selectivity for pyrite and can float copper sulfide minerals under low alkali conditions, for ores with high copper oxidation rates and high secondary copper contents, the copper ions dissolved on the mineral surface during the grinding and flotation process will activate the pyrite, causing its surface to be closer to chalcopyrite, ultimately resulting in poor selectivity for ester collectors and difficulty in obtaining high-quality copper concentrates. As the problems of poor, fine, and impure mineral resources become increasingly serious, the existing flotation reagent system is difficult to achieve efficient utilization of complex copper-iron sulfide ores. Therefore, the development of new collectors with good selectivity to achieve effective separation of copper-iron sulfide minerals under low alkali conditions is the main trend in the comprehensive utilization of complex copper-iron sulfide ore resources.

[0005] The invention patent with application number 202311192338.7 discloses a low-temperature resistant composite collector for separating copper-iron sulfide minerals. The combination of water-phase and oil-phase collectors improves the problem of decreased selectivity of collectors in low-temperature environments, but the effect of copper-sulfur separation is poor, and a large amount of pyrite still enters the concentrate, affecting the quality of copper concentrate. The invention patent with application number 202410288868.X discloses a polymetallic ore separation agent and its preparation method. In addition to being used in the field of copper-sulfur mineral separation, the agent can also be used in lead-zinc flotation separation and gold ore leaching. Although it has strong universality of use, the preparation process is cumbersome, the types of raw materials used are many, and the process is complicated, making it difficult to produce on a large scale industrially. The invention patent with application number 202311199900.9 proposes a method for selective separation of chalcopyrite and pyrite, using lime as an inhibitor, ethanolamine and isopentyl xanthate as collectors to separate chalcopyrite and pyrite, and obtaining a copper concentrate with a grade of 19.75-20.84% ​​and a recovery rate of 89.77-92.98% without adding a frother. The collector is better than conventional xanthate, but the use of advanced xanthate will increase costs. The patent with application number 202311820661.4 discloses a thiocarbamate collector, which generates a class of O-alkyl-N-alkylthiocarbamate alkynyl ester compounds by esterification reaction of multiple raw materials. Compared with Z-200, the use of this collector improves the concentrate yield and gold recovery rate, but the thiocarbamate raw materials are numerous, the preparation process is complicated and the reaction time is long.

[0006] The invention patent with patent application number 202310898826.3 discloses a beneficiation method for high-sulfur and low-copper copper sulfide ore containing secondary copper. The beneficiation method includes grinding, mixed flotation and copper-sulfur separation flotation steps, wherein an organic polyphosphonic acid is added as a pulp adjuster during the grinding process. The organic polyphosphonic acid in the beneficiation method is any one or more of hydroxyethylidene-1,1-diphosphonic acid HEDP, aminotrimethylenephosphonic acid ATMP, and diethylenetriaminepentamethylenephosphonic acid HTPMP, and the addition amount is 50-150g / t ore. The flotation method adopts the beneficiation method of "copper-sulfur mixed flotation-copper-sulfur mixed concentrate regrinding and re-separation". Although the method discloses the addition of aminotrimethylenephosphonic acid ATMP as a pulp adjuster in the copper-sulfur mixed flotation process, its use method only discloses the use of hydroxyethylidene-1,1-diphosphonic acid HEDP as an adjuster, and the role of hydroxyethylidene-1,1-diphosphonic acid HEDP in it is to react with Cu 2+Stable chelates are formed to reduce the activation of pyrite by copper ions. However, the application does not disclose that aminotrimethylenephosphonic acid ATMP can also achieve the same effect as hydroxyethylidene-1,1-diphosphonic acid HEDP. The aminotrimethylenephosphonic acid ATMP of the present invention is used as a component of the combined collector, so that ATMP is adsorbed on the surface of chalcopyrite, making the flotation performance of chalcopyrite stronger. Then, under the combined capture of xanthate, ethylthiocarbamate and a class of polyol fatty acid esters, the process of copper-sulfur mixed flotation-copper-sulfur mixed concentrate regrinding and separation is not required. Only one roughing operation, 3 to 4 fine selections and 2 to 3 scavenging selections are required to obtain high-quality copper concentrate. The present invention has the technical effects of simple flotation process, significantly simplified process and good flotation results. Summary of the invention

[0007] In view of the technical problems existing in the above-mentioned prior art, the present invention provides a method for efficient flotation separation of complex copper-iron sulfide ores. The present invention develops a new type of combined collector as a flotation agent for efficient separation of chalcopyrite and pyrite, and obtains excellent flotation separation effect of complex copper-iron sulfide minerals in a slurry under low-alkali conditions, laying a foundation for obtaining high-quality copper concentrate and subsequent preparation of sulfide concentrate.

[0008] The present invention is achieved through the following technical solutions:

[0009] A method for efficient flotation separation of complex copper-iron sulfide ores, comprising the following steps:

[0010] S1. Prepare a combined collector, wherein the combined collector comprises 75 to 80 parts of aminotrimethylenephosphonic acid, 10 to 15 parts of xanthate, 5 to 10 parts of ethiocarbamate and 0.5 to 1 part of polyol fatty acid ester, and the mass concentration of the combined collector is 30 to 50%;

[0011] S2, pulping, adding 200-800g / t of sulfiding agent to the complex copper-iron sulfide ore, grinding the ore to a fineness of -0.074mm accounting for 65-90%, and then pulping to a slurry with a solid concentration of 25-40wt%;

[0012] S3, flotation, the ore pulp with a solid concentration of 25-40wt% is subjected to a flotation operation of 1 coarse 3-4 fine 2-3 sweeps to obtain copper concentrate and sulfur tailings, wherein a combined collector is used in the flotation process of 1 coarse 3-4 fine 2-3 sweeps.

[0013] The method for preparing the combined collector in S1 is: at room temperature, add 75 to 80 parts of aminotrimethylenephosphonic acid and 10 to 15 parts of xanthate to water and stir for 5 to 10 minutes, then continue to add 5 to 10 parts of ethionamide and stir for 5 to 10 minutes, and finally add polyol fatty acid ester and continue to stir for 15 to 30 minutes to prepare a combined collector with a mass concentration of 30 to 50%.

[0014] ATMP is aminotrimethylenephosphonic acid, its molecular formula is N(CH2PO3H2)3, and its structural unit is as follows:

[0015]

[0016] The molecular formula of ethionamide is: (CH3)2CHOCSNHC2H5.

[0017] The method for preparing the combined collector in S1 is: adding 75-80 parts of ATMP, 10-15 parts of xanthate, and 5-10 parts of ethionamide to water, raising the temperature to 60-70° C., and finally adding 0.5-1 part of polyol fatty acid ester and continuing stirring for 5-10 minutes.

[0018] The polyol fatty acid ester in S1 is monoglyceride (whose molecular formula is C3H7O4-R) or sorbitan fatty acid ester (C7H 11 O6-R).

[0019] The sulfiding agent in S2 is sodium sulfide, sodium hydrosulfide, or any combination of the two.

[0020] The flotation operation of one roughing, 3 to 4 fines and 2 to 3 sweeps in S3 is as follows: a pH adjuster is used to adjust the pH of a slurry with a solid concentration of 25 to 40 wt% to 8 to 10, and an inhibitor, a combined collector and a frother are added to obtain a roughing concentrate and a roughing tailing after flotation, wherein the amount of the inhibitor is 200-1000 g / t, the amount of the combined collector is 30-100 g / t, the amount of the frother is 10-20 g / t, and the action time of each agent in the slurry is 1 to 5 min.

[0021] The flotation operation of 1 roughing, 3 to 4 fines and 2 to 3 sweeps in S3 is as follows: depressants, collectors and frothers are added to the roughing concentrate in sequence, and each acts for 1 to 4 minutes before being refined 3 to 4 times to obtain copper concentrate and refined middlings; wherein the amount of depressants is 50-500 g / t, the combined collector is 10-50 g / t, the amount of frothers is 0-20 g / t, and the amount of reagents used in each refinement operation is halved compared to the previous refinement operation.

[0022] In the flotation operation of 1 rough 3 to 4 fine 2 to 3 sweeps in S3, 2 to 3 sweeps are specifically as follows: inhibitors, collectors and frothers are added to the rough tailings in sequence, and after each of them acts for 1 to 5 minutes, 2 to 3 sweep operations are carried out to obtain swept sulfur tailings and swept ore, wherein the amount of inhibitor used in the first sweep is 40-400g / t, the combined collector is 10-50g / t, the amount of frother is 5-20g / t, and the amount of reagents used in the subsequent sweep operation is 40-50% of that in the previous sweep.

[0023] The pH adjuster is one of sodium carbonate, sodium hydroxide, and lime, or a mixture of several of them in any proportion; the inhibitor is one of sodium sulfite, calcium hypochlorite, and dextrin, or a mixture of several of them in any proportion; and the foaming agent is MIBC or No. 2 oil.

[0024] The above-mentioned concentrated middlings and scavenged middlings are returned to the roughing flotation process.

[0025] The specific technical principle of the present invention is:

[0026] The invention provides a method for efficient flotation separation of complex copper-iron sulfide ores and an application thereof, wherein the ATMP component in the combined collector contains a plurality of phosphate groups, wherein the PO and P=O bonds therein can react with the Fe and Cu elements on the surface of chalcopyrite to form a stable complex, so that the ATMP is adsorbed on the surface of the chalcopyrite, and although the ATMP component can react with the Fe element on the surface of the pyrite, the reaction activity of the iron element on the surface of the pyrite is weaker than that of the iron element on the surface of the chalcopyrite, resulting in a weaker adsorption capacity, thereby realizing the selective separation of the chalcopyrite and the pyrite; the xanthate is a commonly used collector for copper sulfide ores, and the copper component in the material can be recovered to the greatest extent by using the xanthate; the ethiocarbamate is an efficient collector for copper sulfide minerals, has good selectivity for pyrite, and has certain foaming properties, can reduce the amount of the foaming agent added, and further reduce the cost of the agent; the polyol fatty acid ester can reduce the interfacial free energy between the components in the mixed system, thereby reducing the oil-water interfacial tension, so that the immiscible components are uniformly dispersed in the continuous phase in the form of a micron-level dispersed phase. In the combined collector of the present invention, the addition of polyol fatty acid esters can make the ethylthiocarbamate in the oil phase evenly distributed in the water phase in the form of micron-sized droplets, so that the combined collector forms a stable system.

[0027] Adding an appropriate amount of sulfiding agent and grinding it with the copper-iron sulfide ore during the pulping process can effectively sulfidize the surface of the oxidized copper ore, enhance the floatability of the mineral, and allow part of the oxidized copper ore to be captured by the sulfide ore collector.

[0028] Under the action of the above mechanism, the combined collector can selectively adsorb on the surface of chalcopyrite, but weakly or even difficultly adsorb on the surface of pyrite. At the same time, with the help of the inhibitor, the surface of pyrite is made strongly hydrophilic, increasing the difference in hydrophilicity and hydrophobicity between the surfaces of chalcopyrite and pyrite. For complex and difficult-to-select copper-iron sulfide ores, the high oxidation rate and high proportion of secondary copper are significantly improved, and the clean and efficient separation of complex copper-iron sulfide minerals is achieved.

[0029] Compared with the traditional flotation reagent system and the existing process flow, the method of the present invention has the following advantages:

[0030] 1. The combined collector has good solution stability and foaming properties, so that the collector solution can be stored for a long time, which reduces the amount of foaming agent after use. On the other hand, the addition of polyol fatty acid ester makes it easier to form bubbles, prevents liquid film drainage and coalescence, and increases foam persistence, thereby making the flotation foam system more stable.

[0031] 2. The combined collector has good selectivity, especially the strong adsorption of PO and P=O bonds in the ATMP molecule to the Fe and Cu active sites on the surface of chalcopyrite, which enhances the hydrophobicity of the chalcopyrite surface. By using this collector, in a low-alkali environment, with the assistance of an appropriate amount of inhibitor, the difference in hydrophilicity and hydrophobicity between the surface of chalcopyrite and pyrite can be further increased, thereby efficiently separating the copper component from the iron component;

[0032] 3. The collector and process flow can be applied to copper-iron sulfide ores of various properties, and have good effects on complex ores with different oxidation rates and secondary copper occupancies, and have good adaptability.

[0033] 4. The flotation system is a low-alkali environment, and because ATMP has a strong complexing ability with calcium ions, it reduces or even eliminates problems such as scaling of equipment and pipelines, and at the same time creates favorable conditions for further flotation recovery of pyrite minerals in flotation tailings, thereby achieving clean, efficient and comprehensive utilization of complex copper-iron sulfide minerals.

[0034] 5. Under the action of the combined collector and the sulfiding agent, the present invention can obtain copper concentrate with only one coarse 3-4 fine 2-3 sweep flotation operation, and the sulfur tailings can be further recovered from the iron sulfide minerals. The present invention has the technical effects of simple flotation process, significantly simplified process and good flotation results. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a diagram of the mechanism of action of ATMP of the present invention;

[0036] Figure 2 It is a process flow chart of complex copper-iron sulfide ore of the present invention. DETAILED DESCRIPTION

[0037] The present invention will be further described below in conjunction with the accompanying drawings and specific implementation methods.

[0038] Example 1: Flotation test of a complex copper-iron sulfide ore

[0039] Sample 1 of a sulfide ore has a copper grade of 0.57% and a sulfur grade of 8.02%. The main copper-containing mineral is chalcopyrite, the main sulfur-containing mineral is pyrite, and it also contains a small amount of pyrrhotite and a very small amount of arsenopyrite. The proportions of copper oxide and secondary copper are 12% and 4.2% respectively. The specific implementation method is as follows:

[0040] S1. Prepare a combined collector. At room temperature, add 75 parts of aminotrimethylenephosphonic acid and 15 parts of xanthate to water, stir for 5 minutes, then continue to add 9 parts of ethionamide and stir for 10 minutes, and finally add 1 part of sorbitan fatty acid ester and continue stirring for 20 minutes to prepare a combined collector with a mass concentration of 34%;

[0041] S2, pulping, adding 800g / t of sodium sulfide to the complex copper-iron sulfide ore, grinding the ore to a fineness of -0.074mm accounting for 75%, and then pulping the ore to a solid concentration of 28wt%;

[0042] S3, flotation, the pulp with a solid concentration of 28wt% is subjected to a flotation operation of 1 coarse 3-4 fine 2-3 sweep to obtain copper concentrate and sulfur tailings, specifically:

[0043] Primary roughing: pH of the ore pulp with a solid concentration of 28wt% is adjusted to 9.5 with a pH adjuster, and 1000g / t sodium sulfite, 100g / t combined collector and 18g / t No. 2 oil are added. The action time of each reagent in the ore pulp is 3, 3 and 1min respectively. Roughing concentrate and roughing tailings are obtained after flotation;

[0044] 3rd concentration: 400g / t sodium sulfite, 40g / t combined collector, and 5g / t No. 2 oil were added to the rough concentrate for copper concentration. The reagents were used for 3, 3, and 1min respectively. The amount of reagent used in each subsequent concentration operation was halved compared with the previous concentration operation. The concentration was repeated 3 times to obtain copper concentrate and concentrated middlings. The frother was only added in the first concentration.

[0045] Second scavenging: 300g / t sodium sulfite, 50g / t combined collector and 10g / t No. 2 oil were added to the roughing tailings in turn, and the scavenging operation was carried out after 3, 2 and 1min respectively. The dosage of the second scavenging agent was halved compared with the first scavenging to obtain scavenged sulfur tailings and scavenged ore, and the frother was only added in the first scavenging.

[0046] The pH of the flotation process in this embodiment is 9.5. Compared with the existing flotation environment with a pH of 12, the present invention performs flotation under low alkaline conditions. The maximum amount of the frother used in the present invention is 33 g / t. Compared with the conventional amount of the frother used in the prior art of about 40-50 g / t, the amount of the frother used in the present invention is significantly reduced by about 20%. The grade and recovery rate after flotation of the present invention are shown in Table 1.

[0047] Example 2: Secondary flotation test of a complex copper-iron sulfide ore

[0048] Sample 2 of a sulfide ore has a copper grade of 0.43% and a sulfur grade of 9.58%. The main copper-containing mineral is chalcopyrite, the main sulfur-containing mineral is pyrite, and it also contains very small amounts of galena and sphalerite. The proportions of copper oxide and secondary copper are 6.3% and 11.6%, respectively. The specific implementation method is as follows:

[0049] S1. Prepare a combined collector by adding 80 parts of ATMP, 10 parts of xanthate, and 9.2 parts of ethionamide to water, raising the temperature to 60° C., and finally adding 0.8 parts of sorbitan fatty acid ester, and continuing to stir for 10 minutes to prepare a combined collector with a mass concentration of 40%;

[0050] S2, pulping, adding 300g / t of sulfiding agent (sodium sulfide and sodium hydrosulfide in a mass ratio of 2:1) to the complex copper-iron sulfide ore, grinding the ore to a fineness of -0.074mm accounting for 79%, and then pulping to a slurry with a solid concentration of 32wt%;

[0051] S3, flotation, the slurry with a solid concentration of 32wt% is subjected to a flotation operation of 1 coarse 3-4 fine 2-3 sweep to obtain copper concentrate and sulfur tailings, specifically:

[0052] Primary roughing: pH of the pulp with a solid concentration of 32 wt% was adjusted to 9.0 with a pH adjuster, and 200 g / t dextrin, 80 g / t combined collector and 15 g / t MIBC were added. The action time of each reagent in the pulp was 33, 3 and 1 min respectively. Roughing concentrate and roughing tailings were obtained after flotation.

[0053] 3rd concentration: 75g / t dextrin, 40g / t combined collector and 5g / t MIBC were added to the rough concentrate for copper concentration. The reagents were used for 5, 3 and 1min respectively. The dosage of reagents in each subsequent concentration operation was halved compared with that in the previous concentration operation. The concentration was repeated 3 times to obtain copper concentrate and concentrated middlings. The frother was added only in the first concentration.

[0054] Second scavenging: 100g / t dextrin, 40g / t combined collector and 9g / t MIBC were added to the roughing tailings in turn, and the scavenging operation was carried out after each action for 3, 2 and 1min. The dosage of the second scavenging agent was halved compared with the first scavenging to obtain scavenged sulfur tailings and scavenged ore, and the frother was only added in the first scavenging.

[0055] The pH of the flotation process in this embodiment is 9. Compared with the existing flotation environment with a pH of 12, the present invention performs flotation under low alkaline conditions. The maximum amount of the frother used in the present invention is 29 g / t. Compared with the conventional frother used in the prior art of about 40-50 g / t, the amount of the frother used in the present invention is reduced by more than 25%. The grade and recovery rate after flotation of the present invention are shown in Table 1.

[0056] Example 3: Tri-flotation test of a complex copper-iron sulfide ore

[0057] Sample 3 of a sulfide ore has a copper grade of 0.53% and a sulfur grade of 6.14%. The main copper-containing mineral is chalcopyrite, the main sulfur-containing mineral is pyrite, and it contains very small amounts of arsenopyrite and sphalerite. The proportions of copper oxide and secondary copper are 18.2% and 3.5% respectively. The specific implementation method is as follows:

[0058] S1. Prepare a combined collector. At room temperature, add 80 parts of aminotrimethylenephosphonic acid and 12 parts of xanthate to water, stir for 5 minutes, then continue to add 7 parts of ethionamide and stir for 10 minutes, and finally add 1 part of monoglyceride and continue stirring for 20 minutes to prepare a combined collector with a mass concentration of 37%;

[0059] S2, pulping, adding 800g / t of a sulfiding agent (sodium sulfide and sodium hydrosulfide in a mass ratio of 7:3) to the complex copper-iron sulfide ore, grinding the ore to a fineness of -0.074mm accounting for 82%, and then pulping the ore to a solid concentration of 30wt%;

[0060] S3, flotation, the pulp with a solid concentration of 30wt% is subjected to a flotation operation of 1 coarse 3-4 fine 2-3 sweep to obtain copper concentrate and sulfur tailings, specifically:

[0061] Primary roughing: pH of the ore pulp with a solid concentration of 32 wt% was adjusted to 8.5 with a pH adjuster, 100 g / t of inhibitor (sodium sulfite and calcium hypochlorite with a mass ratio of 6:4), 100 g / t of combined collector and 25 g / t of MIBC were added, and the action time of each agent in the ore pulp was 5, 3 and 1 min respectively. Roughing concentrate and roughing tailings were obtained after flotation;

[0062] 3rd concentration: 250+150g / t sodium sulfite and calcium hypochlorite, 30g / t combined collector, and 15g / t MIBC are added to the rough concentrate for copper concentration. The reagents are used for 3, 2, and 1min respectively. The amount of reagent used in each subsequent concentration operation is halved compared with the previous concentration operation. After 3 concentrations, copper concentrate and concentrated middlings are obtained. The frother is only added in the first concentration.

[0063] Second scavenging: 100+100g / t sodium sulfite and calcium hypochlorite, 50g / t combined collector, and 10g / t MIBC were added to the roughing tailings in turn, and the scavenging operation was carried out after each action for 3, 3, and 1min. The dosage of the second scavenging agent was halved compared with the first scavenging to obtain scavenged sulfur tailings and scavenged ore, and the frother was only added in the first scavenging.

[0064] The pH of the flotation process in this embodiment is 8. Compared with the existing flotation environment with a pH of 12, the present invention performs flotation under low alkaline conditions. The maximum amount of the frother used in the present invention is 25 g / t. Compared with the conventional amount of frother used in the prior art of about 40-50 g / t, the amount of the frother used in the present invention is reduced by about 40%. The grade and recovery rate after flotation of the present invention are shown in Table 1.

[0065] Table 1. Experimental results of examples using the method of the present invention

[0066]

[0067] Comparative Example 1:

[0068] The same ore sample as in Example 1 was used, and the flotation process and reagent system except the collector were exactly the same as in Example 1. Ethyl xanthate was used as the collector, and the amount used was the same as the combined collector amount in Example 1. The grade and recovery rate of the obtained copper concentrate are shown in Table 2.

[0069] Comparative Example 2:

[0070] The same ore sample as in Example 2 was used, and the flotation process and reagent system except the collector were exactly the same as in Example 2. Ethyl xanthate was used as the collector, and the amount used was the same as the combined collector amount in Example 2. The copper concentrate grade and recovery rate obtained are shown in Table 2.

[0071] Comparative Example 3:

[0072] The same ore sample as in Example 3 was used, and the flotation process and reagent system except the collector were exactly the same as in Example 3. Ethiocarbamate was used as the collector, and the amount used was the same as the combined collector amount in Example 3. The grade and recovery rate of the obtained copper concentrate are shown in Table 2.

[0073] Comparative Example 4:

[0074] The same ore sample as in Example 1 was used, and the flotation process and reagent system were exactly the same as in Example 1. The difference was that the sulfiding agent sodium sulfide was not added during the S2 pulping process. The grade and recovery rate of the obtained copper concentrate are shown in Table 2.

[0075] Table 2. Comparative flotation concentrate test results using different collectors

[0076]

[0077] The invention discloses a highly efficient flotation separation method for a complex copper-iron sulfide ore and its application, which can selectively adsorb on the surface of chalcopyrite but hardly adsorb on the surface of pyrite, thereby expanding the hydrophilic and hydrophobic differences between the two difficult-to-separate minerals. In addition, the use of the highly efficient flotation collector of the invention patent can achieve clean and efficient separation of target components under low-alkali conditions, easy treatment of mineral processing wastewater, and low cost for subsequent preparation of high-quality sulfur concentrate, and the overall process has the advantages of being green and low-carbon.

[0078] The specific implementation modes of the present invention are described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above implementation modes, and various changes can be made within the knowledge scope of ordinary technicians in this field without departing from the purpose of the present invention.

Claims

1. A method for efficient flotation separation of complex copper-iron sulfide ores, characterized in that The following steps are involved: S1. Prepare a combined collector, wherein the combined collector comprises 75 to 80 parts of aminotrimethylenephosphonic acid, 10 to 15 parts of xanthate, 5 to 10 parts of ethiocarbamate and 0.5 to 1 part of polyol fatty acid ester, and the mass concentration of the combined collector is 30 to 50%; S2, pulping, adding 200-800g / t of sulfiding agent to the complex copper-iron sulfide ore, grinding the ore to a fineness of -0.074mm accounting for 65-90%, and then pulping to a slurry with a solid concentration of 25-40wt%; S3, flotation, the ore pulp with a solid concentration of 25-40wt% is subjected to a flotation operation of 1 coarse 3-4 fine 2-3 sweeps to obtain copper concentrate and sulfur tailings, wherein a combined collector is used in the flotation process of 1 coarse 3-4 fine 2-3 sweeps.

2. The method for efficient flotation separation of complex copper-iron sulfide ores according to claim 1, characterized in that: The method for preparing the combined collector in S1 is: at room temperature, add 75 to 80 parts of aminotrimethylenephosphonic acid and 10 to 15 parts of xanthate to water and stir for 5 to 10 minutes, then continue to add 5 to 10 parts of ethionamide and stir for 5 to 10 minutes, and finally add polyol fatty acid ester and continue to stir for 15 to 30 minutes to prepare a combined collector with a mass concentration of 30 to 50%.

3. The efficient flotation separation method for complex copper-iron sulfide ores according to claim 1, characterized in that: The method for preparing the combined collector in S1 is: adding 75-80 parts of ATMP, 10-15 parts of xanthate, and 5-10 parts of ethionamide to water, raising the temperature to 60-70° C., and finally adding 0.5-1 part of polyol fatty acid ester and continuing stirring for 5-10 minutes.

4. The method for flotation separation and efficient collection of complex copper-iron sulfide ores according to any one of claims 1 to 3, characterized in that: The polyol fatty acid ester in S1 is monoglyceride or sorbitan fatty acid ester.

5. The efficient flotation separation method for complex copper-iron sulfide ores according to claim 1, characterized in that: The sulfiding agent in S2 is sodium sulfide, sodium hydrosulfide, or any combination of the two.

6. The method for efficient flotation separation of complex copper-iron sulfide ores according to claim 1, characterized in that: The flotation operation of one roughing, 3 to 4 fines and 2 to 3 sweeps in S3 is as follows: a pH adjuster is used to adjust the pH of a slurry with a solid concentration of 25 to 40 wt% to 8 to 10, an inhibitor, a combined collector and a frother are added, and a roughing concentrate and a roughing tailing are obtained after flotation, wherein the amount of the inhibitor is 200-1000 g / t, the amount of the combined collector is 30-100 g / t, the amount of the frother is 10-30 g / t, and the action time of each agent in the slurry is 1 to 5 min.

7. The method for efficient flotation separation of complex copper-iron sulfide ores according to claim 6, characterized in that: The flotation operation of 1 roughing, 3 to 4 fines and 2 to 3 sweeps in S3 is as follows: depressants, collectors and frothers are added to the roughing concentrate in sequence, and each acts for 1 to 4 minutes before being refined 3 to 4 times to obtain copper concentrate and refined middlings; wherein the amount of depressants is 50-500 g / t, the combined collector is 10-50 g / t, the amount of frothers is 0-20 g / t, and the amount of reagents used in each refinement operation is halved compared to the previous refinement operation.

8. The method for efficient flotation separation of complex copper-iron sulfide ores according to claim 6, characterized in that: In the flotation operation of 1 rough 3 to 4 fine 2 to 3 sweeps in S3, 2 to 3 sweeps are specifically as follows: inhibitors, collectors and frothers are added to the rough tailings in sequence, and after each of them acts for 1 to 5 minutes, 2 to 3 sweep operations are carried out to obtain swept sulfur tailings and swept ore, wherein the amount of inhibitor used in the first sweep is 40-400g / t, the combined collector is 10-50g / t, the amount of frother is 5-20g / t, and the amount of reagents used in the subsequent sweep operation is 40-50% of that in the previous sweep.

9. The method for flotation separation and efficient collection of complex copper-iron sulfide ores according to any one of claims 6 to 8, characterized in that: The pH adjuster is one of sodium carbonate, sodium hydroxide, and lime, or a mixture of several of them in any proportion; the inhibitor is one of sodium sulfite, calcium hypochlorite, and dextrin, or a mixture of several of them in any proportion; and the foaming agent is MIBC or No. 2 oil.

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