A highly efficient flotation separation method for complex copper-iron sulfide ores

Abstract

The present invention relates to a high-efficiency flotation separation method for complex copper-iron sulfide ore, and belongs to the technical field of flotation reagents. A combined collector is prepared, wherein the components of the combined collector are composed of 75-80 parts of aminotrimethylenephosphonic acid, 10-15 parts of xanthate, 5-10 parts of ethylthiocarbamate, and 0.5-1 part of polyol fatty acid ester, and the mass concentration of the combined collector is 30-50%; 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%; flotation, subjecting the slurry with a solid concentration of 25-40wt% to a flotation operation of one coarse, three-four fine, and two-three sweeps to obtain copper concentrate and sulfur tailings, wherein the combined collector is used in the flotation process of the one coarse, three-four fine, and two-three sweeps. The present invention develops a new type of combined collector as a flotation agent for efficiently separating chalcopyrite and pyrite minerals, thereby achieving excellent flotation separation effect of complex copper-iron sulfide minerals in a slurry under low-alkali conditions.

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 plays a vital role in production activities. During the beneficiation stage, chalcopyrite is the primary target mineral, along with co-existing iron sulfide minerals. Industrial applications primarily utilize flotation technology to selectively recover chalcopyrite. Given the similar surface physical and chemical properties of chalcopyrite and pyrite, both exhibit good floatability in flotation slurries, making their separation difficult. Therefore, achieving selective separation of these two minerals is crucial for the efficient utilization of copper resources.

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

[0004] Industrial copper-sulfur separation primarily uses xanthate as a collector and lime as a pH adjuster and inhibitor. Adjusting the slurry pH to a high alkaline level suppresses pyrite and pyrrhotite. Traditional copper-sulfur separation processes typically use 5-15 kg / t of lime in highly alkaline environments, with a slurry pH > 12. The use of such large amounts of lime inevitably leads to severe scaling of equipment and pipelines, reducing equipment life and hindering long-term production. Even with low-carbon chain ethyl xanthate as a collector, xanthate systems still exhibit a moderate pyrite capture capacity in low-alkaline environments. In recent years, ester collectors such as ethylthiocarbamate have also been increasingly used in the flotation of copper-iron sulfide ores. Although ester collectors have good selectivity for pyrite and can float copper sulfide minerals in 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 minerals, causing their surfaces to become closer to chalcopyrite. This ultimately leads to poor selectivity of ester collectors and difficulty in obtaining high-quality copper concentrates. As problems such as the depletion, fineness, and impurities of mineral resources become increasingly serious, existing flotation reagent systems have difficulty achieving 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 in low-alkali environments is a major 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 and iron sulfide minerals. The combination of water-phase and oil-phase collectors improves the problem of decreased selectivity of collectors in low-temperature environments. However, the effect of copper-sulfur separation is poor, and a large amount of pyrite still enters the concentrate, affecting the quality of the 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 the field of 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 complex, making it difficult to produce on a large scale industrially. Patent application number 202311199900.9 proposes a method for the selective separation of chalcopyrite and pyrite. Using lime as a depressant and ethanolamine and isoamyl xanthate as collectors, the method yields a copper concentrate with a grade of 19.75-20.84% ​​and a recovery of 89.77-92.98% without the addition of a frother. This collector is more effective than conventional xanthates, but the use of higher-grade xanthates increases costs. Patent application number 202311820661.4 discloses a thiocarbamate collector. This collector is produced by esterifying multiple raw materials to form a class of O-alkyl-N-alkylthiocarbamate alkynyl esters. Compared to Z-200, this collector improves concentrate yield and significantly increases gold recovery. However, this thiocarbamate collector requires numerous raw materials, resulting in a complex preparation process and a long reaction time.

[0006] The invention patent with patent application number 202310898826.3 discloses a beneficiation method for high-sulfur, low-copper type 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 method of use only discloses the use of hydroxyethylidene-1,1-diphosphonic acid HEDP as an adjuster, and the role of hydroxyethylidene-1,1-diphosphonic acid HEDP is to react with Cu 2+A stable chelate is formed, reducing the activation of pyrite by copper ions. However, the application does not disclose that aminotrimethylenephosphonic acid (ATMP) can 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 a combined collector, allowing ATMP to be adsorbed on the surface of chalcopyrite, thereby enhancing the flotation performance of chalcopyrite. Then, under the combined capture of xanthate, ethylthiocarbamate, and a class of polyol fatty acid esters, the copper-sulfur mixed flotation-copper-sulfur mixed concentrate regrinding and reseparation process is no longer required. Instead, only a flotation operation of 3 to 4 roughing operations, 2 to 3 scavenging operations, and high-quality copper concentrate can be obtained. The present invention has the technical advantages of a simple flotation process, a significantly simplified process, and good flotation results. Summary of the Invention

[0007] To address the technical problems of the prior art, the present invention provides a highly efficient flotation separation method for complex copper-iron sulfide ores. By developing a novel combined collector as a flotation agent for the efficient separation of chalcopyrite from pyrite, the present invention achieves excellent flotation separation of complex copper-iron sulfide ores in a low-alkali slurry, laying the foundation for obtaining high-quality copper concentrate and the 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 ethionamide, and 0.5 to 1 part of a polyol fatty acid ester, and the mass concentration of the combined collector is 30 to 50%;

[0011] S2, slurrying, 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 slurrying to a solid concentration of 25-40wt%;

[0012] S3, flotation, the slurry 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 as follows: 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 stirring 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 as follows: 75-80 parts of ATMP, 10-15 parts of xanthate, and 5-10 parts of ethionamide are added to water, the temperature is raised to 60-70° C., and finally 0.5-1 part of polyol fatty acid ester is added and stirring is continued for 5-10 minutes.

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

[0019] The sulfiding agent in S2 is one or any combination of sodium sulfide and sodium hydrosulfide.

[0020] The flotation operation of one roughing, 3 to 4 fines and 2 to 3 sweeps in S3 specifically comprises the following steps: adjusting the pH of a slurry having a solid concentration of 25 to 40 wt% to 8 to 10 with a pH adjuster, adding an inhibitor, a combined collector and a frother, and flotating to obtain a roughing concentrate and a roughing tailing, wherein the amount of the inhibitor is 200 to 1000 g / t, the amount of the combined collector is 30 to 100 g / t, and the amount of the frother is 10 to 20 g / t, and the action time of each agent in the slurry is 1 to 5 minutes.

[0021] The flotation operation of 1 roughing, 3 to 4 fines and 2 to 3 sweeps in S3 is as follows: an inhibitor, a collector and a frother are sequentially added to the roughing concentrate, each of which acts for 1 to 4 minutes, and then the concentrate is refined 3 to 4 times to obtain copper concentrate and refined middlings; wherein the amount of the inhibitor is 50-500 g / t, the combined collector is 10-50 g / t, and the amount of the frother is 0-20 g / t, and the amount of the 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, the specific steps are as follows: an inhibitor, a collector and a frother are added to the rougher tailings in sequence, and each of them acts for 1 to 5 minutes, and then 2 to 3 sweep operations are performed to obtain scavenged sulfur tailings and scavenged ore. The amount of inhibitor used in the first sweep is 40-400 g / t, the combined collector is 10-50 g / t, and the frother is 5-20 g / t. 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 principles of the present invention are:

[0026] The present invention provides a high-efficiency flotation separation method for complex copper-iron sulfide ores and its application. The ATMP component in the combined collector contains multiple phosphate groups, wherein the PO and P=O bonds therein can react with Fe and Cu elements on the surface of chalcopyrite to form stable complexes, thereby allowing ATMP to be adsorbed on the chalcopyrite surface. Although the ATMP component can react with the Fe element on the surface of pyrite, the reactivity of the iron element on the surface of pyrite is weaker than that of the iron element on the surface of chalcopyrite, resulting in a weaker adsorption capacity, thereby achieving selective separation of chalcopyrite and pyrite. The xanthate is a commonly used collector for copper sulfide ores and can maximize the recovery of copper components in the material. The ethylthiocarbamate is a high-efficiency collector for copper sulfide ores and has good selectivity for pyrite. It also has certain foaming properties, which can reduce the amount of foaming agent added and thus reduce the cost of the reagent. 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-sized dispersed phase. In the combined collector of the present invention, the addition of polyol fatty acid esters allows the ethylthiocarbamate in the oil phase to be evenly distributed in the aqueous 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 copper-iron sulfide ore during the pulping process can effectively sulfidize the surface of the copper oxide ore, enhance the floatability of the mineral, and allow part of the copper oxide ore to be captured by the sulfide ore collector.

[0028] Through this mechanism, the combined collector selectively adsorbs on the surface of chalcopyrite, while weakly or even barely adsorbing on the surface of pyrite. Simultaneously, the inhibitor renders the pyrite surface strongly hydrophilic, increasing the hydrophilic and hydrophobic differences between the two surfaces. This significantly improves the high oxidation rate and high proportion of secondary copper in complex and difficult-to-separate copper-iron sulfide ores, achieving clean and efficient separation of complex copper-iron sulfide minerals.

[0029] Compared with the traditional flotation reagent system and 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, which enables the collector solution to be stored for a long time and reduces the amount of foaming agent used after use. On the other hand, the addition of polyol fatty acid ester makes it easier to form bubbles and prevents liquid film drainage and coalescence, thereby increasing foam persistence and making the flotation foam system more stable.

[0031] 2. The combined collector exhibits excellent selectivity, particularly due to the strong adsorption of the PO and P=O bonds in the ATMP molecule to the Fe and Cu active sites on the chalcopyrite surface, which enhances the hydrophobicity of the chalcopyrite surface. Using this collector, combined with an appropriate amount of inhibitor in a low-alkaline environment, further increases the difference in hydrophilicity and hydrophobicity between the chalcopyrite and pyrite surfaces, thereby enabling efficient separation of copper and iron components.

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

[0033] 4. The flotation system is a low-alkaline 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. At the same time, it creates favorable conditions for further flotation recovery of pyrite minerals in flotation tailings, achieving clean, efficient and comprehensive utilization of complex copper-iron sulfide minerals.

[0034] 5. Under the action of the combined collector and sulfiding agent, the present invention can obtain copper concentrate with only one coarse 3 to 4 fine 2 to 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 ATMP mechanism of action diagram of the present invention;

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

[0037] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[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-bearing mineral is chalcopyrite, the main sulfur-bearing 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, slurrying, 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 slurrying to a solid concentration of 28wt%;

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

[0043] Primary roughing: A slurry with a solid concentration of 28 wt% was adjusted to pH 9.5 using a pH adjuster. 1000 g / t sodium sulfite, 100 g / t combined collector, and 18 g / t No. 2 oil were added. The various agents were allowed to act on the slurry for 3, 3, and 1 min, respectively. Rougher concentrate and rougher tailings were obtained after flotation.

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

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

[0046] The pH of the flotation process in this embodiment was 9.5. Compared to the conventional flotation environment of pH 12, the present invention performs flotation under low-alkaline conditions. The maximum frother dosage of the present invention is 33 g / t, which is significantly reduced by approximately 20% compared to the conventional frother dosage of approximately 40-50 g / t in the prior art. The grade and recovery after flotation 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-bearing mineral is chalcopyrite, the main sulfur-bearing mineral is pyrite, and there are also 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, slurrying, adding 300g / t of sulfiding agent (sodium sulfide and sodium hydrosulfide with 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 slurrying to a solid concentration of 32wt%;

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

[0052] Primary roughing: A slurry with a solids concentration of 32 wt% was adjusted to pH 9.0 using a pH adjuster. 200 g / t dextrin, 80 g / t combined collector, and 15 g / t MIBC were added. The various agents were allowed to act on the slurry for 33, 3, and 1 min, respectively. Rougher concentrate and rougher tailings were obtained after flotation.

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

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

[0055] The pH of the flotation process in this embodiment was 9. Compared to the conventional flotation environment of pH 12, the present invention performs flotation under low-alkaline conditions. The maximum frother dosage of the present invention is 29 g / t, which is more than 25% lower than the conventional frother dosage of approximately 40-50 g / t in the prior art. The grade and recovery after flotation are shown in Table 1.

[0056] Example 3: Triple 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-bearing mineral is chalcopyrite, the main sulfur-bearing mineral is pyrite, and there are also 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, slurrying, adding 800g / t of 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 slurrying to a solid concentration of 30wt%;

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

[0061] Primary roughing: A slurry with a solids concentration of 32 wt% was adjusted to pH 8.5 using a pH adjuster. 100 g / t of a depressant (sodium sulfite and calcium hypochlorite in a mass ratio of 6:4), 100 g / t of a combined collector, and 25 g / t of MIBC were added. The various agents were allowed to act on the slurry for 5, 3, and 1 min, respectively. Rougher concentrate and rougher tailings were obtained after flotation.

[0062] 3rd cleaning: 250+150g / t sodium sulfite and calcium hypochlorite, 30g / t combined collector, and 15g / t MIBC are added to the rougher concentrate for copper cleaning. The reagents are applied for 3, 2, and 1min, respectively. The amount of reagent used in each subsequent cleaning operation is halved compared to the previous cleaning operation. The cleaning is repeated 3 times to obtain copper concentrate and cleaned middlings. The frother is only added in the first cleaning operation.

[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 sequence, and each was reacted for 3, 3, and 1 min before scavenging. The dosage of the second scavenging agent was halved compared to the first scavenging to obtain scavenged sulfur tailings and scavenged ore. The frother was only added in the first scavenging.

[0064] The pH of the flotation process in this embodiment is 8. Compared to the conventional flotation environment of pH 12, the present invention performs flotation under low-alkaline conditions. The maximum frother dosage of the present invention is 25 g / t, which is approximately 40% lower than the conventional frother dosage of approximately 40-50 g / t in the prior art. The grade and recovery after flotation are shown in Table 1.

[0065] Table 1. Experimental results of the embodiment 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 for 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 copper concentrate grade and recovery rate obtained 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 in the same amount as the combined collector in Example 2. The grade and recovery of the copper concentrate 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 for the collector were exactly the same as in Example 3. Ethiocarbamate was used as the collector in the same amount as the combined collector in Example 3. The grade and recovery of the copper concentrate obtained 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 copper concentrate grade and recovery rate obtained are shown in Table 2.

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

[0076]

[0077] The present invention discloses a highly efficient flotation separation method and application for complex copper-iron sulfide ores, which selectively adsorbs on the surface of chalcopyrite but barely adsorbs on the surface of pyrite, thereby enhancing the hydrophilic and hydrophobic differences between the two difficult-to-separate minerals. Furthermore, the use of this patented high-efficiency flotation collector enables clean and efficient separation of target components under low-alkali conditions, facilitates the treatment of mineral processing wastewater, and reduces the cost of subsequent preparation of high-quality sulfur concentrate, resulting in a green and low-carbon process.

[0078] The above describes the specific embodiments of the present invention in detail with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in this field without departing from the scope 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 75-80 parts of aminotrimethylenephosphonic acid, 10-15 parts of xanthate, 5-10 parts of ethionamide, and 0.5-1 part of polyol fatty acid ester, and the mass concentration of the combined collector is 30-50%; S2, slurrying, 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 slurrying to a solid concentration of 25-40wt%; S3, flotation, the slurry 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 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 as follows: at room temperature, add 75-80 parts of aminotrimethylenephosphonic acid and 10-15 parts of xanthate to water and stir for 5-10 minutes, then continue to add 5-10 parts of ethionamide and stir for 5-10 minutes, and finally add polyol fatty acid ester and continue stirring for 15-30 minutes to prepare a combined collector with a mass concentration of 30-50%.

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 as follows: 75-80 parts of ATMP, 10-15 parts of xanthate, and 5-10 parts of ethionamide are added to water, the temperature is raised to 60-70° C., and finally 0.5-1 part of polyol fatty acid ester is added and stirring is continued for 5-10 minutes.

4. The efficient flotation separation method for 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 one or any combination of sodium sulfide and sodium hydrosulfide.

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

7. The efficient flotation separation method for 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: a depressant, a collector and a frother are sequentially added to the roughing concentrate, each of which acts for 1 to 4 minutes, and then concentrating is performed 3 to 4 times to obtain copper concentrate and concentrating middlings; wherein the amount of depressant is 50-500 g / t, the combined collector is 10-50 g / t, and the amount of frother is 0-20 g / t, and the amount of reagents used in each concentrating operation is halved compared to the previous concentrating operation.

8. The efficient flotation separation method for complex copper-iron sulfide ores according to claim 6, characterized in that: In the flotation operation of 1 roughing 3~4 fine 2~3 sweeps in S3, the specific steps are as follows: adding inhibitor, collector and frother in sequence to the roughing tailings, each acting for 1~5 minutes, and then performing 2~3 sweeping operations to obtain scavenged sulfur tailings and scavenged ore. The amount of inhibitor used in the first sweeping is 40-400g / t, the combined collector is 10-50g / t, and the frother is 5-20g / t. The amount of reagents used in the subsequent sweeping operation is 40-50% of that in the previous sweeping operation.

9. The efficient flotation separation method for 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.

Images