Flotation inhibition of sulfide ores and method for selective flotation separation of pyrite and chalcopyrite

Abstract

The present invention belongs to the field of mineral flotation, and specifically discloses a method for inhibiting the flotation of sulfide ores, wherein a compound of formula 1 is used as an inhibitor to inhibit the flotation of sulfide ores. The present invention also provides a flotation agent and method for inhibiting pyrite and flotating pyrite, comprising the inhibitor, a collector and a frother. In the present invention, the inhibitor can inhibit sulfide ores, but when combined with the collector, it can maintain the targeted inhibition advantage of pyrite and significantly reduce the targeted inhibition advantage of chalcopyrite, so that high-selective separation of pyrite and chalcopyrite can be achieved.

Description

Technical Field

[0001] The invention belongs to the field of mineral flotation, and in particular relates to the field of flotation inhibition of sulfide ores such as pyrite. Background Art

[0002] Copper is a non-ferrous metal that is closely related to human beings. It is widely used in electrical, light industry, machinery manufacturing, construction industry, national defense industry and other fields. It is second only to aluminum in the consumption of non-ferrous metal materials in China (Baidu Encyclopedia). Chalcopyrite is one of the main sources of copper metal.

[0003] Pyrite is the most widely distributed and largest sulfide mineral, and is also the most common gangue mineral of chalcopyrite. Existing traditional collectors for sulfide ores make it difficult to achieve efficient separation of copper-iron sulfide ores. Usually, a large amount of lime is used to adjust the pH of the slurry to a strong alkaline state to inhibit the flotation of pyrite and achieve separation of the two. The use of a large amount of lime will not only cause serious scaling of the pipeline, but also increase the difficulty of treating subsequent mineral processing wastewater. Pyrite that is not completely inhibited will be mixed into the chalcopyrite concentrate product, which will not only cause a decrease in the copper grade, but also cause trouble to the subsequent smelting process. During the smelting process, pyrite will release a large amount of harmful gases such as sulfur dioxide, causing acid rain to harm the environment. Therefore, the development of highly selective pyrite inhibitors is still of great significance. Summary of the invention

[0004] The first object of the present invention is to provide a method for inhibiting the flotation of sulfide ore, aiming to provide a sulfide ore inhibition method.

[0005] The second object of the present invention is to provide a flotation agent that can selectively inhibit pyrite and realize the flotation of chalcopyrite, aiming to improve the separation selectivity of pyrite and chalcopyrite and improve the recovery rate and grade of chalcopyrite.

[0006] The third object of the present invention is to provide a method for selectively flotating and separating pyrite and chalcopyrite by using the flotation agent.

[0007] Sulfide ores such as pyrite are often embedded and coexist with target ores and have a certain natural floatability, which will greatly affect the flotation of target ores. To address this problem, the present invention provides the following improvement scheme:

[0008] A method for inhibiting the flotation of sulfide ore, using a compound of formula 1 as an inhibitor to inhibit the flotation of sulfide ore;

[0009]

[0010] X1 and X2 are independently O, NH, PH, PH3 or CH2;

[0011] The R1 to R4 are independently H, hydroxyl, amino, C1 to C4 short-chain alkyl, or substituted short-chain alkyl; the substituent on the substituted short-chain alkyl is at least one of hydroxyl, amino, cyano, carboxylic acid, amide, ester, and ether;

[0012] Alternatively, the R2 and R3 are combined to form a carbonyl group;

[0013] In the formula 1, the total number of carbon atoms is 3 to 10, and the total number of heteroatoms is greater than or equal to 3.

[0014] In the present invention, Formula 1 is innovatively used as a flotation inhibitor for sulfide ores. Benefiting from the intramolecular synergy of the structure, it can effectively target and bind to the surface of the sulfide ore, thereby effectively inhibiting the flotation of the sulfide ore.

[0015] The present invention has found that the structure of Formula 1 and its high heteroatom / C ratio are the key to synergistically improving the sulfide ore inhibition effect.

[0016] In the present invention, the heteroatom refers to N, O and P in Formula 1.

[0017] In Formula 1 of the present invention, when X1 / X2 is C, R1 and R2 are independently H, hydroxyl, amino, short-chain alkyl or substituted alkyl. X1 and / or X2 are hetero elements (O / N / P), and the substituent connected to the hetero element is preferably H, a short-chain alkyl of C1 to C4, or a substituted short-chain alkyl.

[0018] Preferably, in Formula 1, at least one of X1 and X2 is O or NH; and / or, among R1 to R4, at least one substituent contains O or N. Preferably, the total carbon number of R1 to R4 is less than or equal to 4; for example, it can be H, methyl, hydroxymethyl, ethyl or hydroxyethyl.

[0019] Preferably, in Formula 1, the total number of carbon atoms is 3 to 7; the total number of heteroatoms is 3 to 5; and the ratio of the number of heteroatoms to the number of carbon atoms is greater than or equal to 0.7. In the present invention, the ratio of the number of heteroatoms to the number of carbon atoms refers to the atomic number ratio of the total number of heteroatoms including O, N and P to the total number of carbon elements.

[0020] Preferably, the formula 1 comprises at least one of formula 1-A, formula 1-B, and formula 1-C;

[0021]

[0022]

[0023]

[0024]

[0025] In Formula 1-A and Formula 1-B, R1 and R2 are independently H, methyl, ethyl, hydroxymethyl or hydroxyethyl;

[0026] In formula 1-C, R1 and R2 are independently H, methyl, ethyl, hydroxymethyl or hydroxyethyl;

[0027] In formula 1-D, R1 and R2 are independently H, hydroxyl, hydroxymethyl or hydroxyethyl.

[0028] The present invention has found that the depressant of formula 1 can be applied to inhibit flotation of different types of sulfide ores, for example, the sulfide ore is at least one of pyrite and chalcopyrite.

[0029] As the same inventive concept, the present invention also provides a flotation agent capable of selectively inhibiting pyrite and floating chalcopyrite, comprising the inhibitor of the structure of Formula 1, a collector and a frother.

[0030] Chalcopyrite and pyrite often coexist and both have certain natural floatability, making them difficult to selectively separate. In view of this problem, the present invention innovatively adopts a combination of a depressant of Formula 1, a collector and a frother, which can unexpectedly achieve synergy, unexpectedly highly selectively inhibit pyrite therein, and basically no longer inhibit pyrite, so that highly selective flotation separation of pyrite and chalcopyrite can be achieved.

[0031] The present invention has found that the molecular structure of the inhibitor of formula 1 and the high heteroatom / C ratio are the key to synergistically improving the competitive behavior of the inhibitor and the collector on the surface of pyrite and chalcopyrite. The present invention has found that when the inhibitor of formula 1 and the collector are combined, the inhibitor of formula 1 still has an excellent targeted inhibition advantage on pyrite, and loses the targeted advantage on chalcopyrite, so that high selectivity separation of pyrite and chalcopyrite can be achieved.

[0032] In the present invention, the collector can be a collector for chalcopyrite known in the industry, for example, it can be at least one of conventional sulfide ore collectors such as xanthate collectors, thiol collectors, thiocarbamate collectors, and black medicine collectors; considering the cost of materials, the collector is preferably at least one of ethyl xanthate, propyl xanthate, butyl xanthate, and amyl xanthate.

[0033] The foaming agent is at least one of terpineol, cresol acid, heavy pyridine, methyl isobutyl carbinol, eucalyptus oil, camphor oil, higher alcohols and synthetic foaming agents;

[0034] The molar ratio of the inhibitor, collector and frother is 1×10 -4 ~8×10 -4 :1×10 -5 ~1×10-3 :1×10 -6 ~1×10 -4 ; More preferably, 4×10 -4 ~6×10 -4 :1×10 -4 ~4×10 -4 :1×10 -6 ~1×10 -5 The flotation reagent may not contain components such as dispersants and activators.

[0035] The present invention also provides a flotation separation method for suppressing pyrite and floating chalcopyrite, wherein the minerals to be floated containing pyrite and pyrite are floated in the flotation reagent, the pyrite therein is suppressed, and the chalcopyrite concentrate is obtained by floating.

[0036] The flotation method of the present invention, except for the innovative flotation reagent containing the inhibitor of formula 1, the other operation steps and operation methods can be well known.

[0037] Preferably, in the ore pulp of the flotation process, the concentration of the inhibitor of formula 1 is 1×10 -4 mol / L~8×10 - 4 mol / L; preferably 2×10 -4 mol / L~8×10 -4 mol / L; more preferably 4×10 -4 mol / L~6×10 -4 mol / L.

[0038] There is no special requirement for the dosage of frother, which can be adjusted according to conventional flotation reagents. Considering the cost-effectiveness, 1×10 -6 mol / L~1×10 -4 mol / L, and can be further 1×10 -6 mol / L~5×10 -6 mol / L;

[0039] The amount of collector is 1×10 -5 mol / L~1×10 -3 mol / L; preferably 5×10 -5 mol / L~1×10 -3 mol / L; preferably 1×10 -4 mol / L~5×10 -4 mol / L; more preferably 2×10 -4 mol / L~3×10 -4 mol / L.

[0040] Preferably, the pH value in the flotation stage is 7 to 12, preferably 7 to 10. The present invention has found that at this preferred pH value, in addition to being able to meet the requirements of industrial green flotation reagents, a better separation selectivity of pyrite and chalcopyrite can be obtained. For example, in the present invention, the mixed ore is crushed and slurried to obtain a slurry, and the flotation reagent is added to the slurry for flotation.

[0041] The flotation method of the present invention can realize the efficient separation of Cu-Fe mixed sulfide ores. Under the preferred conditions: when pH=7-10, the recovery rate difference between chalcopyrite and pyrite is higher than 60%.

[0042] Beneficial Effects

[0043] 1. The compound of formula 1 is innovatively used as an inhibitor of sulfide ores. Thanks to its structure and the characteristics of a high heteroatom / C ratio, it can achieve synergy and effectively inhibit the flotation of sulfide ores, especially common pyrite.

[0044] 2. Innovatively, the inhibitor of formula 1 is combined with a collector. Compared with the collector, the inhibitor of formula 1 has a competitive binding advantage for pyrite, and has no targeting advantage for chalcopyrite. In this way, pyrite can be unexpectedly highly selectively inhibited, and chalcopyrite is basically not inhibited, thus achieving highly selective separation of pyrite and chalcopyrite.

[0045] 3. The present invention saves the amount of reagents used for flotation, and the suitable pH for flotation is neutral or alkaline (7-12, preferably 7-10), which meets the requirements of green flotation reagents. More importantly, under green flotation conditions, it can unexpectedly obtain better separation selectivity of pyrite and chalcopyrite, bringing unexpected effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 Flotation flow chart used for the examples;

[0047] Figure 2 It is the recovery data diagram of Example 1;

[0048] Figure 3 This is the recovery data diagram of Example 2.

[0049] Figure 4 This is the recovery data diagram of Example 3.

[0050] Figure 5 This is the recovery data diagram of Example 4.

[0051] Figure 6 This is the recovery data diagram of Example 5. DETAILED DESCRIPTION

[0052] The effects of the present invention are illustrated by taking single minerals of pyrite and chalcopyrite and a binary mixed sulfide ore (1:1) of the two as examples. In the following cases, unless otherwise stated, the components of the minerals used are as shown in Table 1:

[0053] Table 1 Original grades of single minerals of pyrite and chalcopyrite and their binary mixed sulfide ore (1:1)

[0054]

[0055] Note: Cu-Fe mixed sulfide ore is obtained by mixing pyrite and chalcopyrite in a weight ratio of 1:1.

[0056] Example 1

[0057] In order to verify the effect of inhibitors on the separation of pyrite and chalcopyrite single minerals in this case, we used high-purity pyrite and chalcopyrite pure minerals (grades as shown in Table 1) and used Figure 1 The process shown in the figure is to use the inhibitor in this case to suppress different sulfide ores and then add only the frother to carry out the flotation separation process. The flotation process parameters of each group of cases are the same. In this embodiment, no collector is added, and only pineneol is added as the frother (concentration is 2×10 -6 mol / L), the only difference is that the types of flotation sulfide ores are different, so as to compare the flotation and separation effects of the inhibitors in this case.

[0058] The flotation agent of the present invention: the inhibitor is: (Formula 1; dosage see Table 2), the foaming agent is pineol (concentration is 2×10 -6 mol / L).

[0059] use Figure 1 The specific operation is as follows: dry grind the pure mineral ore (particle size of 3mm-0.5mm) for 15min (the particle size after grinding is 0.0740-0.0374mm, dry grinding is carried out in a horizontal ball mill, and the grinding concentration is 35-40%), weigh 2g of the ground single mineral sample (chalcopyrite or pyrite) in each group and pour it into a 40mL flotation tank, add 35mL of deionized water and then add the inhibitor described in this case, add an appropriate amount of deionized water, stir for 3min, add pinene alcohol (the concentration in the slurry is controlled at 2×10 -6 mol / L), stirred for 3 min, and began to scrape bubbles for 3 min. The concentrate was scraped into the concentrate basin along with the foam, and the tailings remained in the flotation tank. The concentrate and tailings were filtered and dried, and their weights were calculated. The recovery rate was calculated. Each group of experiments was carried out in three parallel groups, and the average value was taken and the error (variance) was calculated, which was shown as the error bar in the figure.

[0060] Figure 2Table 2 shows the recovery rates of pure pyrite and chalcopyrite at different reagent dosages in Example 1. (In this case, the inhibitor is used as an inhibitor, pineneol is used as a frother, no other flotation reagents are added, and the pulp pH is 7).

[0061] Depend on Figure 2 It can be seen from the results in Table 2 that, within the tested range of reagent dosage, with the increase in the dosage of the inhibitor of the present invention, the inhibitory ability of the flotation reagent described in this case on pyrite and chalcopyrite is gradually enhanced, which means that the flotation inhibitor described in this case can effectively inhibit the above two sulfide ores at a low dosage. When used without a collector, it is temporarily impossible to achieve efficient flotation separation of Cu-Fe mixed sulfide ores.

[0062] Table 2 Flotation results of Example 1

[0063]

[0064] Example 2

[0065] In order to verify the effect of inhibitor in this case on the separation of pyrite and chalcopyrite when combined with collector, we used high-purity pyrite and chalcopyrite pure minerals (grade as shown in Table 1) and used Figure 1 In the process shown, the inhibitor, collector and frother in this case are used as flotation reagents to suppress different sulfide ores, and then only the frother is added to carry out the flotation separation process. The flotation process parameters of each group of cases are the same, and the only difference is that the types of flotation sulfide ores are different. The difference from Implementation 1 is that the collector and frother (the molar ratio of ethyl xanthate and pineneol is 100:1) are added in this embodiment, so as to compare the separation effects of the flotation reagents and flotation methods in this case.

[0066] The flotation agent of the present invention: the inhibitor is: (Formula 1; dosage is 5×10 -4 mol / L),

[0067] The collector is ethyl xanthate and the foaming agent is pinene alcohol, the ratio of the two is 100:1, and the total dosage is shown in Table 2.

[0068] use Figure 1The process shown in the figure is as follows: dry-grind pure mineral ore (particle size of 3mm-0.5mm) for 15min (particle size after grinding is 0.0740-0.0374mm, dry-grinding is performed in a horizontal ball mill, and grinding concentration is 35-40%), 2g of ground single mineral sample (chalcopyrite or pyrite) is weighed for each group and poured into a 40mL flotation cell, 35mL of deionized water is added, and then the inhibitor described in this case is added, and an appropriate amount of deionized water is added, stirred for 3min, and a collector and a frother are added (the molar ratio of ethyl xanthate and pinene alcohol is 100:1; the total amount is shown in Table 2), stirred for 3min, and scraping and foaming are started. The scraping and foaming last for 3min, and 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 and dried, and then weighed separately to calculate the recovery rate. Each group of experiments is carried out in three parallel groups, and the average value is taken and the error (variance) is calculated, which is shown as the error bar in the figure.

[0069] Figure 3 Table 3 shows the recovery rates of pure pyrite and chalcopyrite at different dosages of reagents in Example 1. (In this case, the inhibitor was used as an inhibitor, pinene alcohol and ethyl xanthate (molar ratio of 100:1, total dosage see Table 3) were used as composite collector-foaming agent, and the pulp pH was 7).

[0070] Depend on Figure 3 It can be seen from the results in Table 3 that, within the tested dosage range of the reagent, when the inhibitor of the present invention is used in combination with the collector, the recovery rate of chalcopyrite is significantly improved with the increase in the dosage of the collector, while the recovery rate of pyrite increases slowly, which means that when the inhibitor of the present invention is used in combination with the collector, efficient separation of chalcopyrite and pyrite can be achieved to obtain a high-grade copper concentrate product.

[0071] Table 3 Flotation results of Example 2 (the amount of inhibitor used in this case is 5×10 -4 mol / L)

[0072]

[0073] Example 3

[0074] By conducting flotation experiments at different solution pH values, the effect of pulp pH on the flotation separation of pyrite and chalcopyrite using the inhibitor of the present invention was explored.

[0075] The flotation agent of the present invention: the inhibitor is: (Formula 1; dosage is 5×10 -4 mol / L), the foaming agent is pineol (concentration is 2×10 -6 mol / L).

[0076] Use high-purity pyrite and chalcopyrite pure minerals (grade as shown in Table 1). Figure 1In the process shown, the flotation process parameters are the same, and the only difference is that different types of sulfide ore single minerals and different pulp pH are used to compare the flotation inhibition effect of the inhibitor of the present invention on pyrite and chalcopyrite single minerals at different pH values.

[0077] use Figure 1 The specific operation is as follows: dry grind pure mineral ore (particle size 3mm-0.5mm) for 15min (particle size after grinding is 0.0740-0.0374mm), dry grind with horizontal ball mill, and the medium filling rate is 30-40%. Weigh 2g of ground single mineral sample in each group and pour it into 40mL flotation tank, add 35mL deionized water and then add inhibitor, the dosage is 5×10 - 4 mol / L, add appropriate amount of deionized water, stir for 3 min, add pH adjuster (sulfuric acid or sodium hydroxide) to adjust the flotation system to a specific pH, stir for 3 min, add pinene alcohol (concentration of 2×10 -6 mol / L), stirred for 3 min, began to scrape bubbles, scraped bubbles for 3 min, the concentrate was scraped into the concentrate basin along with the foam, and the tailings remained in the flotation tank. The concentrate and tailings were filtered and dried, then weighed separately to calculate the recovery rate.

[0078] The pH gradient set in the experiment was: 2, 4, 6, 7, 8, 10, 12.

[0079] Figure 4 The recovery rates of pure pyrite and chalcopyrite at different pH values ​​in Example 3. (The inhibitor concentration in this case is 5×10 -4 mol / L; pH adjusters are sodium hydroxide solution and sulfuric acid solution; frother is pineol, no collector is added, the concentration is 2×10 -6 mol / L).

[0080] Table 4 Flotation results of Example 3

[0081]

[0082] It can be seen from Example 3 that when the collector is not used in conjunction, the inhibitor in this case can effectively inhibit both pyrite and chalcopyrite, but the selectivity is poor, which shows that the inhibitor of the present invention needs to be used in conjunction with the collector to exert the best selective inhibition effect.

[0083] Example 4

[0084] By conducting flotation experiments at different solution pH values, the effect of slurry pH on the flotation separation of pyrite and chalcopyrite when the inhibitor of the present invention is combined with a collector is explored.

[0085] The flotation agent of the present invention: the inhibitor is: (Formula 1; dosage is 5×10-4 mol / L);

[0086] The collector is ethyl xanthate and the foaming agent is pinene alcohol. The molar ratio of the two is 100:1, and the total dosage is 2.5×10 -4 mol / L).

[0087] Use high-purity pyrite and chalcopyrite pure minerals (grade as shown in Table 1). Figure 1 The flotation process parameters are the same as those in the flow chart, except that different types of sulfide ore single minerals and different pulp pH values ​​are used. The difference from Example 3 is that a collector and a frother are added during the flotation process (the molar ratio of ethyl xanthate and pineneol is 100:1, and the total amount is 2.5×10 -4 mol / L), so as to compare the flotation inhibition effect of the inhibitor of the present invention on pyrite and chalcopyrite at different pH values ​​when combined with the collector.

[0088] use Figure 1 The specific operation is as follows: dry grind pure mineral ore (particle size 3mm-0.5mm) for 15min (particle size after grinding is 0.0740-0.0374mm), dry grind with horizontal ball mill, and the medium filling rate is 30-40%. Weigh 2g of ground single mineral sample in each group and pour it into 40mL flotation tank, add 35mL deionized water and then add inhibitor, where the amount is 5×10 - 4 mol / L, add appropriate amount of deionized water, stir for 3 minutes, add pH adjuster (sulfuric acid or sodium hydroxide) to adjust the flotation system to a specific pH and stir for 3 minutes, add collector and frother (ethyl xanthate, pineneol molar ratio of 100:1, total dosage of 2.5×10 -4 mol / L), stirred for 3 min, began to scrape bubbles, scraped bubbles for 3 min, the concentrate was scraped into the concentrate basin along with the foam, and the tailings remained in the flotation tank. The concentrate and tailings were filtered and dried, then weighed separately to calculate the recovery rate.

[0089] The pH gradient set in the experiment was: 2, 4, 6, 7, 8, 10, 12.

[0090] Figure 5 The recovery rates of pure pyrite and chalcopyrite at different pH values ​​in Example 4. (The inhibitor concentration in this case is 5×10 -4 mol / L; pH adjusters are sodium hydroxide solution and sulfuric acid solution; collector and foaming agent (ethyl xanthate, pineneol molar ratio is 100:1, total dosage is 2.5×10 -4 mol / L)).

[0091] Table 5 Flotation results of Example 4

[0092]

[0093]

[0094] As can be seen from Example 4, when the collector is used in combination, the inhibitor in this case achieves selective inhibition of pyrite, especially when the pulp pH is 7-12 (preferably 7-10 in consideration of environmental protection issues), the recovery rate of chalcopyrite is always higher than 80%, while the recovery rate of pyrite is always lower than 30%, and the recovery rates of both are higher than 60%. This further confirms that the inhibitor of the present invention can play a good selective inhibition role when used in combination with the collector, and realizes the efficient separation of copper-iron mixed sulfide ores.

[0095] Example 5

[0096] In order to verify the separation effect of the inhibitor and collector in the mixed sulfide ore of pyrite and chalcopyrite in this case, we used high-purity pyrite and chalcopyrite pure minerals (grade as shown in Table 1), mixed them evenly in a weight ratio of 1:1 to obtain Cu-Fe mixed sulfide ore. Figure 1 The inhibitor concentration in this case is 5×10 -4 mol / L, the collector is ethyl xanthate, and the foaming agent is pineneol, which are mixed at a ratio of 100:1, with a total concentration of 2.5×10 -4 mol / L, pH 7-10.

[0097] The flotation agent of the present invention: the inhibitor is: (Formula 1; dosage is 5×10 -4 mol / L),

[0098] The collector is ethyl xanthate and the foaming agent is pinene alcohol, which are mixed at a ratio of 100:1, with a total concentration of 2.5×10 - 4 mol / L;

[0099] Flotation pulp pH = 7-10.

[0100] The specific operation is as follows: pure mineral ore (particle size of 3mm-0.5mm) is dry-ground for 15min (particle size after grinding is 0.0740-0.0374mm, horizontal ball mill is used for dry grinding, and medium filling rate is 30-40%), 2g of mixed ore sample after grinding and mixing in proportion is weighed for each group and poured into a 40mL flotation tank, 35mL of deionized water is added, and then the inhibitor of the present invention is added, and an appropriate amount of deionized water is supplemented, and the inhibitor concentration is 5×10 -4 mol / L, the pH of the slurry was 4 / 10; stirred for 3 min, and the collector and frother were added (total concentration was 2.5×10 -4mol / L), stirred for 3 minutes, and began to scrape bubbles. The concentrate was scraped into the concentrate basin along with the foam, and the tailings remained in the flotation tank. The concentrate and tailings were filtered and dried, and then weighed separately. The grade of the concentrate was tested and the recovery rate was calculated.

[0101] The specific mixing ratio of the Cu-Fe mixed sulfide ore described in this case is as follows:

[0102] In this case, the Cu-Fe mixed sulfide ore: 1g of pyrite and 1g of chalcopyrite were stirred at room temperature for 5 minutes to make the minerals fully mixed for use.

[0103] The grades of the Cu-Fe mixed sulfide ore in this case are shown in Table 1.

[0104] Figure 6 Table 6 shows the recovery rate of each mineral and the grade of the corresponding metal in the flotation concentrate product of the mixed ore of Example 5 when the slurry pH is 7-10.

[0105] Table 6 Chalcopyrite flotation results of Example 5 (slurry pH is 4-7)

[0106]

[0107] Figure 6 As can be seen from the results in Table 6, when the inhibitor concentration is 5×10 -4 mol / L, the concentration of flotation collector is 2.5×10 -4 mol / L, the flotation method of the present invention has excellent separation effect on Cu-Fe mixed sulfide ores when the pulp pH is 7-10.

[0108] Under the condition of pH=7-10, the inhibitory effect of the flotation reagent of the present invention on pyrite in Cu-Fe mixed sulfide ore is much stronger than that on chalcopyrite (recovery rate is higher than 80%, grade is higher than 27%). According to the flotation results, the flotation reagent of the present invention significantly improves the flotation separation effect of pyrite and chalcopyrite, the grade of the useful mineral chalcopyrite is significantly improved, and the pyrite concentrate is also enriched in the tailings.

[0109] Example 6

[0110] In order to verify the influence of the regulating substituents in the inhibitor structure of the present invention on the selective inhibition of pyrite, the following groups of compounds with different structures were selected as inhibitors, and the collector and inhibitor were used as flotation reagents. High-purity pyrite and chalcopyrite pure minerals (grade as shown in Table 1) were still used, and were mixed evenly in a ratio of 1:1 to obtain Cu-Fe mixed sulfide ore. Figure 1 The process shown.

[0111] Flotation reagents: The following inhibitors (the concentration in the pulp is 5×10-4 mol / L);

[0112] Collector and inhibitor (xanthate and pineneol were mixed in a molar ratio of 100:1, with a total concentration of 2.5×10 - 4 mol / L);

[0113] Flotation pulp pH=7.

[0114] Experimental group 1: inhibitor a:

[0115] Experimental group 2: inhibitor b:

[0116] Experimental group 3: inhibitor c:

[0117] Experimental group 4: inhibitor d:

[0118] Comparative group 1: inhibitor e:

[0119] Comparative group 2: inhibitor f:

[0120] Comparative group 3: inhibitor g:

[0121] Comparative group 4: Inhibitor h: starch

[0122] The specific operation is as follows: pure mineral ore (particle size of 3mm-0.5mm) is dry-ground for 15min (particle size after grinding is 0.0740-0.0374mm, horizontal ball mill is used for dry grinding, and medium filling rate is 30-40%), 2g of mixed ore sample after grinding and mixing in proportion is weighed for each group and poured into a 40mL flotation tank, 35mL of deionized water is added, and then the inhibitor of the present invention is added, and an appropriate amount of deionized water is supplemented, and the inhibitor concentration is 5×10 -4 mol / L, the pH of the slurry was 7; stirred for 3 minutes, and a composite collector-foaming agent (prepared by mixing pinene alcohol and ethyl xanthate at a ratio of 1:100, with a concentration of 2.5×10 -4 mol / L), stirred for 3 minutes, and began to scrape bubbles. The concentrate was scraped into the concentrate basin along with the foam, and the tailings remained in the flotation tank. The concentrate and tailings were filtered and dried, and then weighed separately. The grade of the concentrate was tested and the recovery rate was calculated.

[0123] In this case, the Cu-Fe mixed sulfide ore: 1.0g pyrite and 1.0g chalcopyrite were stirred at room temperature for 5 minutes to make the minerals fully mixed for use;

[0124] The grade of the Cu-Fe mixed sulfide ore in this case is shown in Table 1.

[0125] Table 7 Flotation results of Example 6 (slurry pH is 7)

[0126]

[0127] Table 7 shows the recovery rate of each sulfide ore and the grade of the corresponding metal in the flotation concentrate of Cu-Fe mixed sulfide ore in Example 6 (the concentration of each inhibitor in this case is 5×10 4 mol / L, the total concentration of collector and frother is 2.5×10 -4 mol / L (obtained by compounding pinene alcohol and ethyl xanthate at a ratio of 1:100, pH 7). It can be seen from Table 7 that when the pulp pH = 7, the structure of the compound of formula A, formula B, formula C or formula D contained in the flotation reagent of the present invention is within the limit conditions of the present invention (inhibitor ad), and a good index is obtained in the separation of Cu-Fe mixed sulfide ores. When the compound structure exceeds the range described in the present invention (inhibitor e: the total number of carbons of R1 and R2 is far more than 3, the product index of the chalcopyrite concentrate obtained by the flotation separation of Cu-Fe mixed sulfide ores (chalcopyrite recovery rate or Cu grade) is significantly reduced.

[0128] According to the test results, it can be seen that the less the total number of R1 and R2 carbons, the better the product index of the chalcopyrite concentrate obtained by flotation separation of Cu-Fe mixed sulfide ore. The above results show that the inhibitor of the present invention has a very significant effect on the selective inhibition of pyrite when used in conjunction with a collector (i.e., the flotation reagent of the present invention), and the index of the chalcopyrite concentrate product can be further improved by regulating the substituents in the inhibitor compound of the present invention.

[0129] In addition, it can be seen from experimental groups 1-4 and comparative groups 1-4 that controlling the total carbon number and the heteroatom content and ratio can synergistically improve the separation selectivity of iron-copper sulfide ores.

Claims

1. A flotation agent for selectively suppressing pyrite and flotating chalcopyrite, characterized in that: Contains inhibitors, collectors and frothers; The inhibitor comprises at least one of Formula 1-A, Formula 1-B, Formula 1-C, and Formula 1-D; Formula 1-A Formula 1-B Formula 1-C Formula 1-D In Formula 1-A and Formula 1-B, R1 and R2 are independently H, methyl, ethyl, hydroxymethyl or hydroxyethyl; In formula 1-C, R1 and R2 are independently H, methyl, ethyl, hydroxymethyl or hydroxyethyl; In formula 1-D, R1 and R2 are independently H, hydroxyl, hydroxymethyl or hydroxyethyl.

2. The flotation agent for suppressing pyrite and flotating chalcopyrite according to claim 1, characterized in that: The collector is at least one of conventional sulfide ore collectors such as xanthate collectors, mercaptan collectors, thiocarbamate collectors, and black medicine collectors; The foaming agent is at least one of terpineol, cresol acid, heavy pyridine, methyl isobutyl carbinol, eucalyptus oil, camphor oil, higher alcohols and synthetic foaming agents; The molar ratio of the inhibitor, collector and frother is 1 × 10 -4 ~ 8 × 10 -4 :1 × 10 -5 ~ 1× 10 -3 :1 × 10 -6 ~ 1 × 10 -4 .

3. A flotation separation method for suppressing pyrite and flotating chalcopyrite, characterized in that: The mineral to be floated, which contains pyrite and chalcopyrite, is floated in the flotation agent described in claim 1 or 2, the pyrite therein is suppressed, and the chalcopyrite concentrate is obtained by flotation.

4. The flotation separation method for suppressing pyrite and flotating chalcopyrite according to claim 3, characterized in that: In the slurry of the flotation process, the concentration of the inhibitor of formula 1 is 1 × 10 -4 mol / L ~ 8 × 10 -4 mol / L; The amount of foaming agent is 1 × 10 -6 mol / L ~ 1 × 10 -4 mol / L; The amount of collector was 1 × 10 -5 mol / L ~ 1 × 10 -3 mol / L.

5. The flotation separation method for suppressing pyrite and flotating chalcopyrite according to claim 3 or 4, characterized in that: The pH value in the flotation stage is 7~12.

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