Collecting agent, flotation reagent and method for flotation separation of chalcopyrite and pyrite

Abstract

The invention belongs to the field of mineral flotation, and particularly discloses a collecting agent, a flotation reagent and a method for flotation separation of chalcopyrite and pyrite, and the collecting agent comprises a compound shown in the formula 1 (# imgabs 0 #), a compound shown in the formula 2 (# imgabs 1 #), a compound shown in the formula 3 (# imgabs 2 #) and a compound shown in the formula 4 (# imgabs 3 #) according to the weight ratio of (2-5): (2-5): (1-5): (1-3). According to the collecting agent, high-selectivity separation of chalcopyrite and pyrite can be achieved under the mild and green conditions through combined control over the components and proportions of the compounds shown in the formula 1, the formula 2, the formula 3 and the formula 4.

Description

Technical Field

[0001] The present invention belongs to the field of mineral flotation, and particularly relates to the technical field of flotation of copper-iron sulfide ores. Background Art

[0002] Chalcopyrite often occurs in natural ore deposits in close symbiosis with sulfide minerals such as pyrite (FeS2), showing similar floatability characteristics during the flotation process, making it difficult for traditional flotation processes to effectively separate copper and sulfur minerals. This not only results in a low grade of copper concentrate but also causes a large amount of sulfur elements to enter the smelting system, increasing the subsequent environmental protection treatment pressure.

[0003] In current industrial practice, the flotation separation of copper-iron sulfide ores remains a difficult problem in the industry. Conventional xanthate collectors have unsatisfactory selectivity for chalcopyrite and pyrite. To obtain qualified copper concentrate, concentrators generally use the high-alkali lime method for process regulation. This method increases the pH value of the pulp by adding a large amount of lime and uses hydroxide ions to form a hydrophilic iron hydroxide film on the surface of pyrite to achieve mineral inhibition. Although this process is relatively mature and the copper-sulfur separation effect is relatively significant, there are many inherent defects. For example, a large amount of lime usage leads to an increase in reagent costs; a high-alkali environment easily causes problems such as an increase in pulp viscosity and poor foam stability, affecting the stability of flotation indexes; excessive lime will cause pipeline scaling and equipment corrosion, increasing maintenance costs; high-alkalinity wastewater needs to be neutralized before it can meet the discharge standards, increasing environmental protection costs; in addition, recent research has found that a strongly alkaline environment will partially inhibit the flotation activity of chalcopyrite, resulting in a decrease in copper recovery.

[0004] Developing a highly selective collector for chalcopyrite is the key path to breaking through the bottleneck of existing technologies. An ideal new collector should be able to specifically bind to the copper active sites on the surface of chalcopyrite through molecular structure design under neutral or weakly alkaline (pH 7-9) conditions, while avoiding interaction with pyrite. This targeted flotation mechanism is expected to significantly reduce the use of pyrite inhibitors such as lime, which can not only reduce reagent costs but also simplify the process flow. At the same time, the supporting low-alkali copper-sulfur separation method can significantly improve the quality of tailings water and promote clean production. Therefore, researching and developing highly efficient selective collectors and supporting low-alkali processes is of great practical significance for improving the utilization efficiency of copper resources and promoting the green transformation of the beneficiation industry. Summary of the Invention

[0005] The first object of the present invention is to provide a collector for flotation separation of chalcopyrite-pyrite, aiming to improve the flotation separation selectivity of chalcopyrite and pyrite.

[0006] The second object of the present invention is to provide a flotation reagent for flotation separation of chalcopyrite-pyrite.

[0007] The third object of the present invention is to provide a method for flotation separation of chalcopyrite-pyrite.

[0008] Chalcopyrite and pyrite are often intergrown, and their properties are similar. In addition, the copper grade is usually low and the iron grade is high, which will further increase the difficulty of flotation separation. Aiming at the problem that chalcopyrite and pyrite are difficult to be selectively flotation separated, the present invention provides the following improvement scheme:

[0009] A collector for flotation separation of chalcopyrite - pyrite, comprising Compound of Formula 1, Compound of Formula 2, Compound of Formula 3 and Compound of Formula 4 in a weight ratio of 2 - 5:2 - 5:1 - 5:1 - 3;

[0010] Formula 1;

[0011] Formula 2;

[0012] Formula 3;

[0013] Formula 4;

[0014] In Formulas 1 - 4, R1 is an alkyl group with 1 - 8 carbon atoms; R2 is an alkyl group with 1 - 8 carbon atoms or a phenyl group; R3 and R4 are independently an alkyl group with 1 - 8 carbon atoms; R5 is an alkyl group with 1 - 8 carbon atoms or a phenyl group;

[0015] M is H, NH4, Na or K.

[0016] The present invention innovatively provides a brand - new selective collector for chalcopyrite. It innovatively combines Formulas 1 - 4, and further coordinates with the combined control of the groups and ratios of Formulas 1 - 4, so as to achieve synergy and significantly improve the flotation separation efficiency of chalcopyrite and pyrite; excellent separation selectivity of chalcopyrite - pyrite can be obtained at a lower dosage of the reagent and the original pulp pH (the original pulp is neutral or weakly alkaline). The collector described in the present invention does not need to rely on a high - alkalinity environment like the prior art during the flotation process, so as to effectively reduce the flotation cost and the adverse impact of the beneficiation wastewater on the environment. Moreover, better Cu - Fe separation indexes can be obtained.

[0017] The combined control of Formulas 1 - 4 and the groups and ratios in the present invention is the key to synergistically improving the flotation selectivity of chalcopyrite and pyrite.

[0018] In the present invention, the alkyl group can be a straight - chain or branched - chain alkyl group.

[0019] In the present invention, R1 is an alkyl group with 1 - 4 carbon atoms. Further, it can be an alkyl group such as methyl, ethyl, etc.

[0020] The research of the present invention shows that for Formula 1 with optimized R1, its combination with other components and ratios can further strengthen the synergy of the components, contribute to further improving the separation selectivity of chalcopyrite - pyrite, and improving the flotation effect under neutral and weak alkaline conditions.

[0021] R2 is an alkyl group with 1 - 4 carbon atoms. The research of the present invention also finds that for the compound of Formula 2 with optimized R2, its combination with other components and ratios can further strengthen the separation selectivity of chalcopyrite and pyrite under neutral and weak alkaline conditions.

[0022] R3 and R4 are independently alkyl groups with 2 - 4 carbon atoms.

[0023] R5 is an alkyl group with 2 - 4 carbon atoms. The research of the present invention also finds that for the compound of Formula 4 with optimized R5, its combination with other components and ratios can further strengthen the separation selectivity of chalcopyrite and pyrite under neutral and weak alkaline conditions.

[0024] In the present invention, the combined control of the components, groups, and ratios of Formulas 1 - 4 enables high - selectivity flotation separation of chalcopyrite - pyrite under more environmentally friendly pulp conditions (such as neutral and weak alkaline conditions, i.e., pH = 7 - 9).

[0025] Preferably, the weight ratio of the compound of Formula 1, the compound of Formula 2, the compound of Formula 3, and the compound of Formula 4 is 2 - 4:3 - 4:1 - 3:1 - 2; more preferably 2.5 - 3.5:2.5 - 3.5:2.5 - 3:1. The research of the present invention shows that under this preferred combination ratio, the combined synergy effect between components can be further strengthened, and better separation selectivity of sulfide ores can be obtained.

[0026] The present invention also provides a flotation reagent for flotation - separating chalcopyrite - pyrite, which contains the collector described in the present invention and also contains a foaming agent.

[0027] The foaming agent can be a component known in the industry with foaming ability, such as including but not limited to 2 # oil, terpineol, BK201, methyl isobutyl carbinol (MIBC), methyl amyl alcohol, 2 - ethylhexanol, C6 - C8 mixed fatty alcohols, mixed hexanol (P - MPA), C5 - C7 mixed secondary alcohols, 1, 1, 3 - triethoxybutane (TEB), methyl alcohol ether, ethyl alcohol ether, butyl alcohol ether, C5 - C6 and C5 - C9 mixed fatty acid ethyl esters, diethyl phthalate, and BK, RB, 730 series foaming agents, etc., at least one of them.

[0028] The present invention also provides a method for flotation separation of chalcopyrite and pyrite. The ore to be selected containing chalcopyrite and pyrite is mixed with flotation reagents for rough selection to obtain rough concentrate of chalcopyrite and rough tailings of pyrite. Among them, the flotation reagents contain the collector described in the present invention.

[0029] The flotation method described in the present invention is applicable to the associated ore of chalcopyrite and pyrite with any grade and characteristics. Especially for the ore to be selected with relatively poor existing grade, by using the collector described in the present invention for flotation, the selective flotation of chalcopyrite - pyrite can also be achieved under neutral and weakly alkaline conditions.

[0030] For example, in the present invention, in the ore to be selected, the grade of copper can be low - grade chalcopyrite, and its copper content can be less than 0.5%.

[0031] During the flotation process described in the present invention, the dosage of the selective collector for chalcopyrite can be reasonably adjusted according to the ore grade and type, throughput, treatment process, flotation cost and economic benefits, etc.

[0032] Preferably, during the rough selection process, the dosage of the collector is 10 - 300 g / t, preferably 20 - 200 g / t; more preferably 40 - 120 g / t; even more preferably 50 - 90 g / t. In the present invention, due to the combined synergy of the formulas 1 - 4, excellent collection rate and selectivity can be obtained with a lower dosage of the collector.

[0033] In the flotation method described in the present invention, the flotation reagents are also allowed to contain a frother. In the present invention, the dosage of the frother can be 1 - 50 g / t; preferably 1 - 20 g / t; even more preferably 5 - 10 g / t.

[0034] The pH during the rough selection process is 6 - 10, more preferably 7 - 9; even more preferably 7.5 - 8.5.

[0035] In the present invention, the rough selection can be carried out based on the original neutral or weakly alkaline condition of the pulp (without additional pH regulation). Of course, for some special types of minerals, it is also allowed to use conventional pH regulation means to adjust the pH during the flotation process to neutral or weakly alkaline.

[0036] In the present invention, the rough concentrate of chalcopyrite can be subjected to cleaning treatment based on conventional ideas. In addition, the rough tailings of pyrite can also be subjected to scavenging treatment based on conventional means.

[0037] Beneficial effects

[0038] 1. The present invention innovatively combines the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in a specified ratio in a synergistic manner, so that the chalcopyrite selective collector can be endowed with good collecting ability and selectivity, and can significantly improve the flotation separation effect of chalcopyrite and pyrite. The research also shows that by optimizing the control of R1-R5 in Formulas 1-4, the synergy between components can be further optimized, and the flotation separation efficiency and selectivity of chalcopyrite and pyrite can be unexpectedly further improved.

[0039] 2. In the present invention, due to the good synergy of the component compounds of the chalcopyrite selective collector, better flotation indexes can be obtained under lower collector dosage and more environmentally friendly pulp pH conditions (neutral and weakly alkaline, i.e., pH = 7-9). It can improve the resource utilization rate of copper sulfide ore and the environmental protection of the flotation process, can greatly reduce the use of pyrite inhibitors such as lime, reduce the flotation cost while reducing the adverse effects of inhibitors on copper flotation, and can also avoid the generation of high-alkalinity ore dressing wastewater and reduce the adverse effects on the environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 Flotation flowcharts of single minerals and mixed ores for Examples 1-3.

[0041] Figure 2 Flotation results of single minerals with different collector dosages for Example 1.

[0042] Figure 3 Flotation results of single minerals at different pH values for Example 2.

[0043] Figure 4 Flotation flowcharts of actual ores for Examples 4-8 and Comparative Examples 1-2. DETAILED DESCRIPTION OF THE INVENTION

[0044] Taking single minerals of chalcopyrite and pyrite, artificial mixed ore (weight ratio of chalcopyrite to pyrite is 1:1), and copper ore from a certain concentrator in Jiangxi (actual ore) as examples to illustrate the effects of the present invention. In the following cases, unless otherwise specified, the compositions of the minerals used are as shown in Table 1:

[0045]

[0046] In the following cases, the flotation pH refers to the pH of the pulp in the flotation stage, and the acidic regulator in the pH regulator can be hydrochloric acid, and the alkaline regulator can be sodium hydroxide.

[0047] In addition, each collector can be in the hydrogen form (in Formulas 1-4, the agent with M being H) and / or the salt form (in Formulas 1-4, M is NH4 + , Na + or K +). During the flotation process, there is a correlation between the hydrogen form and salt form of the reagent and the pH of the flotation stage. For example, when the pH of the flotation stage is acidic, the reagent in the flotation system mainly or entirely exists in the hydrogen form. When the pH of the flotation stage is alkaline, part or all of M in the reagent exists in the salt form of alkaline cations. In the present invention, as an example, in the following cases, the reagents initially used in Formulas 1 to 3 are in the Na salt form (refer to -S with the following structure - expression).

[0048] Example 1

[0049] To verify the flotation effect of the described chalcopyrite selective collector, first, single chalcopyrite and pyrite pure minerals (Table 1) were used, and the Figure 1 shown single-mineral flotation process was adopted. The chalcopyrite selective collector of this case (also simply referred to as the combined collector, selective collector, or collector in the present invention) was used for collection. Except for the dosage of the chalcopyrite selective collector, the flotation process parameters in each group of cases were the same. In this example, terpineol was added as a foaming agent, and hydrochloric acid and sodium hydroxide were used as pH adjusters.

[0050] The chalcopyrite selective collector in this example:

[0051] Compound of Formula 1 ( ), compound of Formula 2 ( ), compound of Formula 3 ( ), and compound of Formula 4 ( ); the weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 3:3:3:1.

[0052] Adopt the Figure 1 shown process. The specific operation is as follows: The single pure mineral ore in Table 1 (particle size 3 mm - 0.5 mm) was dry ball-milled. Each group weighed 2.0 g of the ground single-mineral sample with a particle size in the range of 0.074 - 0.038 mm and poured it into a 40 mL flotation cell. The pulp was adjusted to pH = 8 by adding a pH adjuster. After adding 35 mL of deionized water, the chalcopyrite selective collector of this example was added, and an appropriate amount of deionized water was supplemented. After stirring for 3 min, terpineol (dosage 1 × 10 -6 mol / L) was added, and after stirring for 3 min, foaming started. Foaming was carried out for 3 min. The concentrate was scraped into the concentrate basin with the foam, and the tailings remained in the flotation cell. The concentrate and tailings were filtered, dried, and weighed respectively to calculate the recovery rate. Each group of experiments was carried out in three parallel groups, and the average value was taken. Figure 2 Recovery rates of chalcopyrite and pyrite pure minerals in Example 1 under different dosages of the chalcopyrite selective collector.

[0053] As Figure 2As shown, in this embodiment, the composite reagent has a selective collecting ability for chalcopyrite when the pulp pH is 8, while its collecting ability for pyrite is very weak. At a low reagent dosage (1 × 10 -5 mol / L), chalcopyrite can be efficiently collected (recovery rate exceeds 98%), while the recovery rate of pyrite is only 30%. The difference in recovery rates between the two is up to 68%, which confirms that the chalcopyrite selective collector in this embodiment has excellent flotation performance.

[0054] Example 2

[0055] To verify the influence of regulating the pulp pH on the flotation effect of the chalcopyrite selective collector, high-purity chalcopyrite and pyrite pure minerals (Table 1) were used, and the single-mineral flotation process shown in Figure 1 was adopted. The chalcopyrite selective collector of this case was used to collect the pure minerals. The dosage of the chalcopyrite selective collector was 1 × 10 -5 mol / L. Except for the different pulp pH values, the flotation process parameters of each group of cases were the same. In this embodiment, terpineol was added as a frother (dosage was 1 × 10 -6 mol / L), and hydrochloric acid and sodium hydroxide were used as pH adjusters.

[0056] Selective collector: Compound of Formula 1 ( ), Compound of Formula 2 ( ), Compound of Formula 3 ( ), and Compound of Formula 4 ( ); the weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 3:3:3:1.

[0057] Adopt the process shown in Figure 1 . The specific operation is as follows: Dry-grind the pure mineral ore (particle size 3 mm - 0.5 mm). Weigh 2.0 g of single-mineral samples with a particle size in the range of 0.074 - 0.038 mm for each group and pour them into a 40 mL flotation cell. Add pH adjusters to adjust the pulp pH to 6, 7, 8, 9, or 10 respectively. After adding 35 mL of deionized water, add the chalcopyrite selective collector of this embodiment, supplement an appropriate amount of deionized water, stir for 3 min, add terpineol (dosage is 1×10 -6 mol / L), stir for 3 min, start scraping foam, scrape foam for 3 min, the concentrate is scraped into the concentrate basin with the foam, and the tailings remain in the flotation cell. The concentrate and tailings are filtered, dried, and weighed respectively to calculate the recovery rate. Each group of experiments is carried out in three parallel groups, and the average value is taken. Figure 3 Recovery rates of each sulfide mineral under different pulp pH conditions in Example 2.

[0058] As shown in Figure 3As shown, the selectivity of the composite agent in this embodiment is much lower under acidic conditions than under neutral or alkaline conditions. When the pulp pH is 5 - 12 (preferably pH = 6 - 10 considering the effect; further preferably pH = 7 - 9 considering environmental protection), the chalcopyrite selective collector in this embodiment can effectively separate chalcopyrite and pyrite. After being flotation-separated by the chalcopyrite selective collector, chalcopyrite is concentrated in the flotation concentrate, and pyrite is concentrated in the flotation tailings. The difference in the recovery rates of the two is in the range of 58% - 74%. The results of Example 2 also confirm that the chalcopyrite selective collector in this embodiment is applicable under a relatively wide range of pH conditions, has excellent flotation performance under the environmental pulp conditions of neutral and weak alkalinity, and can achieve differential flotation of chalcopyrite and pyrite.

[0059] Example 3

[0060] To verify the flotation performance of the chalcopyrite selective collector (also simply referred to as the collector) when dealing with the flotation of mixed ores, high-purity chalcopyrite and pyrite pure mineral samples with particle sizes in the range of 0.074 - 0.038 mm were compounded in a ratio of 1:1 to obtain an artificial mixed ore (Table 1). Using Figure 1 the shown mixed ore flotation process, the mixed ore was collected using the chalcopyrite selective collector of this case. The dosage of the chalcopyrite selective collector was 1 × 10 -5 mol / L, the pulp pH = 6 - 9, and the other flotation process parameters of each group of cases were the same. In this embodiment, terpineol was added as the frother (dosage: 1 × 10 -6 mol / L), and hydrochloric acid and sodium hydroxide were used as pH adjusters.

[0061] Selective collector: Compound of Formula 1 ( ), Compound of Formula 2 ( ), Compound of Formula 3 ( ), and Compound of Formula 4 ( ); the weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 3:3:3:1.

[0062] Using Figure 1 the shown process, the specific operation is as follows: Weigh 2.0 g of the mixed ore sample for each group and pour it into a 40 mL flotation cell. Add the pH adjuster to adjust the pulp to pH = 6 - 9. After adding 35 mL of deionized water, add the chalcopyrite selective collector of this embodiment, supplement an appropriate amount of deionized water, stir for 3 min, and add terpineol (dosage: 1 × 10 -6(mol / L), stir for 3 min, start skimming the foam, skim the foam for 3 min, the concentrate is skimmed to the concentrate basin with the foam, the tailings remain in the flotation cell, the concentrate and tailings are weighed separately after filtration and drying, and the recovery rate is calculated. Each group of experiments is carried out in three parallel groups, and the average value is taken. Table 2 shows the recovery rate and grade of the mixed ore in Example 3 under different pulp pH conditions.

[0063]

[0064] As shown in Table 2, when dealing with the artificially mixed ore, the selective collector for chalcopyrite of this example achieved good copper-iron separation effect. When the pulp pH is 6, the recovery rate of chalcopyrite is 95.76%, the recovery rate of pyrite is 36.22%, meanwhile the Cu grade is 24.52%, and the Fe grade is 12.49%. When the pulp pH is 7, the recovery rate of chalcopyrite is 98.75%, the recovery rate of pyrite is 30.23%, meanwhile the Cu grade is 25.88%, and the Fe grade is 10.66%. When the pulp pH is 8, the recovery rate of chalcopyrite is 98.89%, the recovery rate of pyrite is 28.39%, meanwhile the Cu grade is 26.26%, and the Fe grade is 10.15%. When the pulp pH is 9, the recovery rate of chalcopyrite is 97.18%, the recovery rate of pyrite is 24.33%, meanwhile the Cu grade is 27.03%, and the Fe grade is 9.11%. The above results show that the selective collector for chalcopyrite of the present invention can achieve efficient flotation separation of chalcopyrite and pyrite under relatively broad and environmentally friendly pH conditions (pH = 6 - 9).

[0065] Example 4

[0066] Taking an actual ore from a copper mine in Jiangxi Province (the elemental composition is shown in Table 1) as an example to further illustrate the effect of the present invention. The flotation method can refer to Figure 4 the actual ore flotation process shown. After crushing the actual ore, take 500 g of ore sample for ball milling and wet grinding, then pour it into the flotation cell, add the specified amount of composite flotation reagent, supplement an appropriate amount of water, use the pH adjuster to adjust the pulp to pH = 8, the foaming agent is 2 # #2 oil (the dosage is 5 g / t), the dosage of the selective collector for chalcopyrite (also simply referred to as the collector or combined collector in the present invention) is 80 g / t for all, stir with aeration for 3 min, start the automatic skimming of the scraper. Concentrates 1, 2, 3, and 4 are all rough concentrate products. After being skimmed to their respective concentrate basins with the foam respectively, the roughing tailings remain in the flotation cell. Each concentrate and tailings are filtered by suction and dried, then weighed separately. The metal grades of each rough concentrate and tailings in the roughing are detected and the recovery rate is calculated. The total grade of the rough concentrates is calculated by calculating the recovery rate of each rough concentrate grade. Each condition is repeated 3 times for the experiment, and the average value is taken. The results are shown in Table 3.

[0067] Selective collector for chalcopyrite in this embodiment: Compound of Formula 1 ( ), Compound of Formula 2 ( ), Compound of Formula 3 ( ), and Compound of Formula 4 ( ); The weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 3:3:3:1.

[0068]

[0069] As can be seen from the results of Example 4, under the preferred substitution of substituents and the preferred ratio in the selective collector for chalcopyrite of the present invention, excellent flotation separation effects can be obtained for copper ores. The Cu grade in the rough concentrate 1 is 13.04%, which is 28 times enriched compared with the original ore of 0.47%. At the same time, the recovery rate of chalcopyrite is 91.76%, and the recovery rate of pyrite is only 13.56%. The difference in recovery rates between the two can reach 78.20%. The total recovery rate of chalcopyrite rough concentrate can reach 96.33%, and the total recovery rate of pyrite rough concentrate is 28.76%. The difference between the two is 67.57%.

[0070] Example 5

[0071] Compared with Example 4, the difference is only that: the components in the selective collector are changed, and the experimental groups are respectively:

[0072] A: Only replace Compound of Formula 1 in the selective collector with an equal weight of ;

[0073] B: Only replace Compound of Formula 2 in the selective collector with an equal weight of ;

[0074] C: Only replace Compound of Formula 3 in the selective collector with an equal weight of ;

[0075] D: Only replace Compound of Formula 4 in the selective collector with an equal weight of ;

[0076] Note: -C4H9 refers to n-butyl;

[0077] Other components and ratios are the same as those of the selective collector in Example 4; The flotation method is also the same as that in Example 4, and the flotation results are shown in Table 4.

[0078]

[0079] As can be seen from Table 4, when the substituents are restricted within the scope required by the present invention, good flotation indexes can be maintained, and high chalcopyrite recovery rate and high Cu grade can be better balanced.

[0080] Example 6

[0081] Compared with Example 4, the only difference is that in this example, the selective collector for chalcopyrite is: Compound of Formula 1 ( ), Compound of Formula 2 ( ), Compound of Formula 3 ( ), and Compound of Formula 4 ( ); the weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 4:4:1:1. The flotation process is the same as that in Example 4, and the results are shown in Table 5:

[0082]

[0083] As can be seen from the results of Example 6, under the preferred substitution of substituents and the preferred ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in the selective collector for chalcopyrite of the present invention, excellent flotation separation effect can be obtained for copper ore. The Cu grade in the rough concentrate 1 is 11.59%, which is 25 times enriched compared with the original ore of 0.47%. At the same time, the recovery rate of chalcopyrite is 93.86%, and the recovery rate of pyrite is only 18.23%. The difference in the recovery rates of the two can reach 75.63%. The total recovery rate of chalcopyrite rough concentrate can reach 98.07%, and the total recovery rate of pyrite rough concentrate is 37.08%. The difference between the two is 60.99%.

[0084] Example 7

[0085] Compared with Example 4, the only difference is that in this example, the selective collector for chalcopyrite is: Compound of Formula 1 ( ), Compound of Formula 2 ( ), Compound of Formula 3 ( ), and Compound of Formula 4 ( ); the weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 2:3:3:2.

[0086] Note: -C4H9 refers to n-butyl; -C5H 11 refers to n-pentyl; the flotation method is also the same as that in Example 4, and the flotation results are shown in Table 6.

[0087]

[0088] As can be seen from the results of Example 7, under the preferred substitution of substituents and the preferred ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in the selective collector for chalcopyrite of the present invention, excellent flotation separation effect can be obtained for copper ore. The Cu grade in the rough concentrate 1 is 11.12%, which is 24 times enriched compared with the original ore of 0.47%. At the same time, the recovery rate of chalcopyrite is 94.33%, and the recovery rate of pyrite is only 19.22%. The difference in the recovery rates of the two can reach 75.11%. The total recovery rate of chalcopyrite rough concentrate can reach 98.88%, and the total recovery rate of pyrite rough concentrate is 37.79%. The difference between the two is 61.09%.

[0089] Example 8

[0090] Compared with Example 4, the difference is only that the dosages of the chalcopyrite selective collector and the frother are changed. The experimental groups are as follows: the dosage of the chalcopyrite selective collector is 60 g / t, and the dosage of the frother is 10 g / t. Others are the same as in Example 4. The results are shown in Table 7.

[0091]

[0092] As can be seen from Table 7, when the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in the chalcopyrite selective collector of the present invention are substituted with preferred substituents and in preferred ratios, excellent flotation separation effects can be obtained for copper ores. The Cu grade in the rough concentrate 1 is 15.46%, which is 33 times enriched compared with the original ore of 0.47%. At the same time, the recovery rate of chalcopyrite is 89.67%, and the recovery rate of pyrite is only 10.11%. The difference in the recovery rates of the two can reach 79.56%. The total recovery rate of the chalcopyrite rough concentrate can reach 95.33%, and the total recovery rate of the pyrite rough concentrate is 22.80%. The difference between the two is 72.53%.

[0093] In summary, the comprehensive flotation performance of the chalcopyrite selective collector of the present invention is good, which can improve the grade of the copper rough concentrate while ensuring a high copper recovery rate.

[0094] Comparative Example 1

[0095] Compared with Example 4, the difference is only that the composition of the chalcopyrite selective collector is changed. The experimental groups are as follows:

[0096] Group 1: Lack of Formula 1, and the ratios of the other remaining components and the total collector dosage are the same as in Example 4;

[0097] Group 2: Lack of Formula 2, and the ratios of the other remaining components and the total collector dosage are the same as in Example 4;

[0098] Group 3: Lack of Formula 3, and the ratios of the other remaining components and the total collector dosage are the same as in Example 4;

[0099] Group 4: Lack of Formula 4, and the ratios of the other remaining components and the total collector dosage are the same as in Example 4;

[0100] Group 5: The weight ratio of Formula 1, Formula 2, Formula 3, and Formula 4 is 1:1:4:4, and the total collector dosage is the same as in Example 4;

[0101] Group 6: The weight ratio of Formula 1, Formula 2, Formula 3, and Formula 4 is 2:2:2:4, and others are the same as in Example 4;

[0102] Group 7: Lack of Formula 3 and Formula 4, that is, the weight ratio of Formula 1, 2, 3, and 4 is 5:5:0:0, and the total collector dosage is the same as in Example 4;

[0103] Group 8: Formulas 1 and 4 are missing, that is, the weight ratio of Formulas 1, 2, 3, and 4 is 0:5:5:0, and the total collector dosage is the same as in Example 4;

[0104] Group 9: Formulas 1 and 2 are missing, that is, the weight ratio of Formulas 1, 2, 3, and 4 is 0:0:5:5, and the total collector dosage is the same as in Example 4;

[0105] Group 10: Formulas 2 and 4 are missing, that is, the weight ratio of Formulas 1, 2, 3, and 4 is 5:0:5:0, and the total collector dosage is the same as in Example 4;

[0106] The flotation results of each group are shown in Table 8.

[0107]

[0108] It can be seen from the examples and comparative examples that when the selected ratios of the compounds of Formulas 1, 2, 3, and 4 in the chalcopyrite selective collector of the present invention are not within the defined range, the flotation separation effect of chalcopyrite and pyrite in copper ore becomes worse, the enrichment ratio is not higher than 19, and it is impossible to balance the recovery rate and grade of chalcopyrite in the rough concentrate 1.

[0109] Comparative Example 2

[0110] Compared with Example 4, the difference is only that the components in the selective collector are changed. The experimental groups are as follows:

[0111] A: Only replace Formula 1 in the selective collector with , and other components and ratios are the same as in Example 4;

[0112] B: Only replace Formula 2 in the collector with , and other components and ratios are the same as in Example 4;

[0113] C: Only replace Formula 3 in the selective collector with , and other components and ratios are the same as in Example 4;

[0114] D: Only replace Formula 4 in the selective collector with , and other components and ratios are the same as in Example 4;

[0115] E: Only replace Formula 1 in the selective collector with , and other components and ratios are the same as in Example 4;

[0116] F: Only replace Formula 4 in the selective collector with , and other components and ratios are the same as in Example 4;

[0117] The results of each group are shown in Table 9.

[0118]

[0119] As can be seen from Table 9, when the preferred substituent range of the present invention is exceeded, the flotation index significantly decreases, and it is difficult to balance the high recovery rate of chalcopyrite and the high grade of Cu.

[0120] Based on the above-mentioned examples and comparative examples, it can be seen that when the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in the chalcopyrite selective collector of the present invention are compounded in a preferred ratio, the comprehensive flotation performance of the flotation reagent can be effectively improved, and the copper grade can be increased while maintaining a good copper recovery rate. If the compounding ratio exceeds the defined range or a certain compound is missing, the flotation performance of the chalcopyrite selective collector significantly deteriorates, and the recovery rate and grade of the rough concentrate both decrease significantly.

[0121] When the preferred substituents are selected for the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in the chalcopyrite selective collector of the present invention, excellent flotation separation effects can be obtained for copper ores, and the recovery rate and grade of pyrite in the rough concentrate are both very low. However, when the substituent structures of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in the chalcopyrite selective collector of the present invention exceed the scope described in the present invention, the recovery rate of chalcopyrite and the Cu grade in the obtained rough concentrate both decrease significantly, that is, the flotation index deteriorates.

[0122] Based on the above results, it is shown that the chalcopyrite selective collector of the present invention can achieve green and efficient flotation enrichment of chalcopyrite in copper ores, and the flotation index (i.e., recovery rate and grade) can be further improved by adjusting the substituents in the compounds of Formula 1, Formula 2, Formula 3, and Formula 4, the compounding ratio of each compound, and the pulp pH value described in the present invention.

Claims

1. A collector for flotation separation of chalcopyrite - pyrite, characterized in that, Comprising a compound of formula 1, a compound of formula 2, a compound of formula 3 and a compound of formula 4 in a weight ratio of 2-5:2-5:1-5:1-3; Formula 1; Formula 2; Formula 3; Formula 4; In formulas 1 to 4, R1 is an alkyl group having 1 to 8 carbon atoms; R2 is an alkyl group having 1 to 8 carbon atoms or a phenyl group; R3 and R4 are each independently an alkyl group having 1 to 8 carbon atoms; R5 is an alkyl group having 1 to 8 carbon atoms or a phenyl group; M is H, NH4, Na or K.

2. The collector according to claim 1, characterized in that, R1 is an alkyl group having 1 to 4 carbon atoms; R2 is an alkyl group having 1 to 4 carbon atoms; R3 and R4 are each independently an alkyl group having 2 to 4 carbon atoms; R5 is an alkyl group having 2 to 4 carbon atoms.

3. The collector according to claim 1, characterized in that, In the collector, the weight ratio of the compound of formula 1, the compound of formula 2, the compound of formula 3 and the compound of formula 4 is 2-4:3-4:1-3:1-2.

4. The collector according to claim 1, characterized in that, In the collector, the weight ratio of the compound of formula 1, the compound of formula 2, the compound of formula 3 and the compound of formula 4 is 2.5-3.5:2.5-3.5:2.5-3:

1.

5. A flotation reagent for separating chalcopyrite - pyrite, characterized in that, Comprising the collector according to any one of claims 1 to 4, and further comprising a frother.

6. A method for flotation separation of chalcopyrite - pyrite, characterized in that, Mixing the mineral to be selected containing chalcopyrite and pyrite with flotation reagents for rough selection to obtain a rough concentrate of chalcopyrite and a rough tailing of pyrite; wherein, the flotation reagents contain the collector according to any one of claims 1 to 4.

7. The method for flotation separation of chalcopyrite - pyrite according to claim 6, characterized in that, During the rough selection process, the dosage of the collector is 10-300 g / t.

8. The method for flotation separation of chalcopyrite - pyrite according to claim 6, characterized in that, The flotation reagents further contain a frother, wherein the dosage of the frother is 1-50 g / t.

9. The method for flotation separation of chalcopyrite - pyrite according to claim 6, characterized in that, The pH during the rough selection process is 6-10.

10. The method for flotation separation of chalcopyrite - pyrite according to any one of claims 6 to 9, characterized in that, It further includes a process of cleaning the rough concentrate of chalcopyrite, and / or a process of scavenging the rough tailing of pyrite.

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