Composite collector and method for flotation of sulfide ore

Abstract

The present invention belongs to the field of mineral flotation, and specifically discloses a composite collector and method for flotation of sulfide ores. The composite collector comprises a compound of Formula 1 (#imgabs0#), a compound of Formula 2 (#imgabs1#), a compound of Formula 3 (#imgabs2#), and a compound of Formula 4 (#imgabs3#) in a weight ratio of 2-7:1-2:1-3:1-3; R1-R4 are each independently an alkyl group, aryl group, heteroaryl group, alkenyl group, alkynyl group, substituted alkyl group, or substituted phenyl group having 2-8 carbon atoms; and M is H, NH4, Na, or K. The present invention provides a novel composite collector, which can significantly improve the flotation separation efficiency of complex sulfide ores through the combined control of the components and ratios of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4; in addition, it can also improve the pH sorting sensitivity, and thus the selective sorting of different complex sulfide ores can be achieved based on simple pH regulation.

Description

Technical Field

[0001] The invention belongs to the field of mineral flotation, and in particular relates to the technical field of flotation of complex sulfide ores. Background Art

[0002] Sulfide minerals, as important metal resources, play a pivotal role in modern industrial and economic development. For example, galena (PbS), sphalerite (ZnS) and chalcopyrite (CuFeS 2 ) are the main sources of global lead, zinc and copper production respectively. Lead is widely used in battery manufacturing, radiation protection and alloy production, while zinc is important in galvanizing, corrosion protection, alloy manufacturing and chemical raw materials. Chalcopyrite is a key ore for copper metal production due to its high copper content and good flotation performance. However, sulfide ores often contain a variety of the above sulfide minerals, as well as a large amount of gangue sulfide minerals such as pyrite (FeS 2 ), the composition is very complex, resulting in low flotation separation efficiency.

[0003] As one of the most critical and widely used technologies in the field of mineral separation, flotation has become the main means to achieve large-scale ore separation and enrichment due to its high efficiency, economy and strong adaptability. In the flotation process, the collector, as the core agent for adjusting the hydrophobicity of the mineral surface, directly affects the recovery rate and grade of the target mineral, and its performance determines the effect of the flotation process. Traditional sulfide ore collectors such as xanthate collectors have poor selectivity and still need to be used in conjunction with a large amount of inhibitors to achieve separation. For example, the high-alkali lime method not only causes scaling in the pipeline, but also the highly alkaline mineral processing wastewater also harms the environment. Although the new single sulfide ore collectors developed in recent years have improved selectivity, they still have problems such as high cost and difficulty in balancing collection capacity and selectivity. Therefore, the development of efficient, green and economical new composite collectors is of great significance to improving the comprehensive resource utilization rate of complex sulfide ores. Summary of the invention

[0004] The first object of the present invention is to provide a composite collector for flotation of sulfide ores, aiming to improve the universality and separation selectivity of difficult-to-separate sulfide ores.

[0005] A second object of the present invention is to provide a method for flotation of sulfide ore, aiming to improve the separation selectivity of sulfide ore.

[0006] A composite collector for flotation of sulfide ore, 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 2-7:1-2:1-3:1-3;

[0007] Formula 1;

[0008] Formula 2;

[0009] Formula 3;

[0010] Formula 4;

[0011] The R 1 ~R 4 is independently an alkyl, aryl, heteroaryl, olefin, alkynyl, substituted alkyl or substituted phenyl group having 2 to 8 carbon atoms; wherein M is H, NH 4 , Na or K.

[0012] The present invention innovatively provides a new composite collector, which can significantly improve the flotation separation efficiency of complex sulfide ores based on the combined synergy within the molecules of each component and between the molecules of each component through the combined control of the components and the proportions of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4; in addition, it can also improve the pH sorting sensitivity, and thus can achieve the selective sorting of different complex sulfide ores based on simple pH regulation.

[0013] The combined control of formula 1 to formula 4 and the ratio described in the present invention is the key to synergistically improving the universality and separation selectivity of sulfide ores. On this basis, further optimization of the composition and ratio of the collector will help further improve the universality and separation selectivity of sulfide ores.

[0014] In Formula 1 to Formula 4 of the present invention, the alkyl group is a straight chain or branched chain alkyl group. The aryl group is, for example, a benzene ring, or an aromatic ring formed by combining two or more benzene rings. The heterocyclic aromatic group includes, for example, a five-membered or six-membered heterocyclic aromatic group, such as a furan ring, a thiophene ring, a thiazole ring, an imidazole ring, a pyridine ring, etc. The substituted alkyl group is a group with a substituent on the alkyl group; the substituted phenyl group is a group with a substituent on the benzene ring, and the substituent is, for example, at least one of an alkyl group, an alkoxy group, a halogen group, a nitro group, etc.

[0015] Preferably, the R 1 , R 2 The present invention shows that the preferred R 1 , R 2 The combined synergistic effects within and between component molecules can be further improved, and the pH sensitivity and the separation selectivity of different sulfide ores can be further improved.

[0016] In the present invention, the R 3 , R 4 Alone for C 3 ~C 6 of alkyl.

[0017] In the present invention, the combined control of the components and proportions of Formulas 1 to 4 is the key to optimizing their pH sensitivity and thus improving the selective separation effect of different sulfide ores. 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 5 to 7: 1: 1 to 2: 1 to 2. The present invention has shown that under this preferred combination and combination ratio, the combined synergistic effect between the components can be further enhanced, and a better sulfide ore separation selectivity can be obtained.

[0018] The present invention also provides a method for flotation of sulfide ore, wherein the sulfide ore to be selected and a flotation agent containing a collector are mixed, floated, and flotation concentrate and flotation tailings are collected, wherein the collector is the composite collector described in the present invention.

[0019] In the present invention, the sulfide ore to be selected comprises at least one of galena, chalcopyrite, sphalerite and pyrite.

[0020] Wherein, when the sulfide ore to be selected contains galena, the galena is enriched in the flotation concentrate after flotation by the composite collector;

[0021] When the sulfide ore to be selected contains chalcopyrite, the chalcopyrite is enriched in the flotation concentrate after flotation by the composite collector;

[0022] When the sulfide ore to be selected contains pyrite, the pyrite is enriched in the flotation tailings after flotation by the composite collector;

[0023] When sphalerite is contained in the sulfide ore to be selected, it is enriched in the flotation concentrate when the flotation pH is below 7.5 (preferably 6-7); it is enriched in the flotation tailings when the flotation pH is greater than 7.9 (preferably 8-10).

[0024] An optional solution of the present invention (Scheme a): the sulfide ore to be selected is mineral A, which comprises mineral A1 and mineral A2, wherein the mineral A1 comprises at least one of galena and chalcopyrite; and the mineral A2 comprises pyrite;

[0025] Mineral A is floated at a pH of 5 to 10 (preferably 6 to 10), wherein mineral A1 is enriched in the flotation concentrate and mineral A2 is enriched in the flotation tailings. In scheme A of the present invention, efficient selective separation between lead-iron sulfide ores and copper-iron sulfide ores can be achieved, and the pH in the flotation stage is relatively mild, which is conducive to industrial application.

[0026] Another optional solution of the present invention (Scheme b): the sulfide ore to be selected is mineral B, which comprises mineral B1 and mineral B2, wherein the mineral B1 comprises sphalerite; and the mineral B2 comprises pyrite;

[0027] When the pH of the flotation is 5-7 (preferably 6-7), the mineral B1 is enriched in the flotation concentrate, and the mineral B2 is enriched in the flotation tailings. The scheme of the present invention can achieve the separation of zinc and iron minerals.

[0028] In scheme b of the present invention, mineral B1 further comprises mineral B1a, and the mineral B1a comprises at least one of chalcopyrite and galena;

[0029] When the pH of flotation is 5-7 (preferably 6-7), mineral B1 is enriched in the flotation concentrate, and mineral B2 is enriched in the flotation tailings;

[0030] When the pH of flotation is 8-10, mineral B1a in mineral B1 is enriched in the flotation concentrate, and sphalerite and mineral B2 in mineral B1 are enriched in the flotation tailings. The scheme b of the present invention can achieve the selective separation of zinc-lead-iron, zinc-copper-iron, and zinc-copper-lead-iron minerals.

[0031] Another optional solution of the present invention (Scheme c): the sulfide ore to be selected is mineral C, which includes mineral C1 and mineral C2, wherein the mineral C1 includes at least one of chalcopyrite and galena, and the mineral C2 includes sphalerite; under the flotation condition of pH 8-10, mineral C1 is enriched in the flotation concentrate, and mineral C2 is enriched in the flotation tailings. The solution of the present invention can achieve the selective separation of lead-zinc and copper-zinc minerals.

[0032] In summary, the process described in the present invention, based on the combined control of the components and proportions of the composite collector, can achieve selective separation of different sulfide ores by adjusting the pH, and has excellent collection effect, collection selectivity and universality.

[0033] In the flotation process described in the present invention, the dosage of the composite collector can be reasonably adjusted according to the grade and type of the mineral, the processing volume and processing flow, the flotation cost and economic benefits, etc. The dosage of the composite collector in the flotation process is 10 g / t or more; preferably, the dosage of the composite collector is 20-200 g / t; further preferably, the dosage of the composite collector is 40-120 g / t. In the present invention, thanks to the combined synergy of Formula 1 to Formula 4, excellent capture rate and selectivity can be obtained at a lower dosage of the collector.

[0034] In the flotation method of the present invention, the flotation reagent may also contain a frother. In the present invention, the frother may be a component with frother ability known in the industry, such as but not limited to 2 # Oil, terpineol, BK201, methyl isobutyl carbinol (MIBC), methyl amyl alcohol, 2-ethylhexanol, C 6 ~C 8Mixed fatty alcohols, mixed hexyl alcohols (P-MPA), C 5 ~C 7 Mixed secondary alcohol 1, 1, 3-triethoxybutane (TEB), methyl alcohol ether, ethyl alcohol ether, butyl alcohol ether, C 5 ~C 6 and C 5 ~C 9 At least one of mixed fatty acid ethyl ester, diethyl phthalate, and BK, RB, 730 series foaming agents, etc. In the present invention, the amount of the foaming agent may be no more than 50 g / t; further, the amount of the foaming agent may be no more than 20 g / t, for example, further may be 1-20 g / t.

[0035] In the present invention, the pH regulator for adjusting the pH value in the flotation stage may include at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, calcium oxide, calcium hydroxide, lime, potassium hydroxide, potassium carbonate, ammonia water, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, citric acid, acetic acid, phosphoric acid, etc.

[0036] Beneficial Effects

[0037] 1. The innovative research of the present invention shows that the compounds of Formula 1, Formula 2, Formula 3 and Formula 4 are combined in a specified ratio to give the composite collector good collection ability and selectivity, which can significantly improve the directional separation effect of complex sulfide ores. The research also shows that 1 , R 2 The group is preferably controlled to be phenyl or substituted phenyl, R 3 , R 4 The group control is C 3 ~C 6 When an alkyl radical is added, the synergy between the components can be further optimized, which unexpectedly further improves the flotation separation efficiency of complex sulfide ores.

[0038] 2. In the present invention, thanks to the good synergy of the components of the composite collector, better flotation indexes can be obtained at a lower collector dosage and a greener and more environmentally friendly pulp pH condition, which can significantly improve the resource utilization rate of complex sulfide ores. In addition, the present invention can expand the applicable system of the composite collector by pH regulation, for example, when the pH is 6 to 10, it is suitable for the flotation separation of lead-iron and copper-iron sulfide ores, when the pH is 6 to 7, it is suitable for the flotation separation of zinc-iron sulfide ores, and when the pH is 8 to 10, it is suitable for the flotation separation of lead-zinc sulfide ores. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The flotation process of single mineral, mixed ore and actual ore for the embodiments and comparative examples;

[0040] Figure 2The single mineral flotation result of Example 1 (composite collector dosage experiment);

[0041] Figure 3 This is the single mineral flotation result of Example 2 (slurry pH condition experiment). DETAILED DESCRIPTION

[0042] The effects of the present invention are illustrated by taking single minerals and mixed minerals of pyrite and chalcopyrite and a high-sulfur lead-zinc ore from a concentrator in Yunnan Province as examples. In the following cases, unless otherwise stated, the composition of the minerals used is as shown in Table 1:

[0043] ;

[0044] In the following cases, the flotation pH mentioned refers to the pH of the pulp during the flotation stage.

[0045] In addition, each collector may be a hydrogen-type (agents in Formulas 1 to 4 where M is H) and / or a salt-type (agents in Formulas 1 to 4 where M is NH 4 + 、Na + or K + ). During the flotation process, the hydrogen form and salt form of the reagent are related to 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 the M in the reagent exists in the salt form of alkaline cations. In the present invention, as an illustrative method, in the following cases, the reagent used initially in Formula 1 and Formula 2 can be in the hydrogen form. The reagent used initially in Formula 3 and Formula 4 is in the Na salt form (refer to the following structure -S - ).

[0046] In the following cases, the acidic regulator in the pH regulator may be hydrochloric acid, and the alkaline regulator may be sodium hydroxide.

[0047] Example 1

[0048] In order to verify the flotation effect of the composite collector on various sulfide minerals, single pure minerals of galena, sphalerite, chalcopyrite and pyrite (Table 1) were first used. Figure 1 The single mineral flotation process shown in the figure uses the composite collector of this case to collect different sulfide minerals. Except for the amount of the composite collector, the flotation process parameters of each group of cases are the same. In this example, pineneol is added as a frother (the amount is 10 g / t), and hydrochloric acid and sodium hydroxide are used as pH adjusters.

[0049] The composite collector of this embodiment: the compound of formula 1 ( ), the compound of formula 2 ( ), the compound of formula 3 ( ) and the compound of formula 4 ( ); The weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 5:1:2:2.

[0050] use Figure 1 The process shown in the figure is as follows: dry-grind the single pure mineral ore (particle size of 3 mm~0.5 mm) in Table 1 for 15 min (the particle size after grinding is 0.074~0.038 mm, and dry grinding is performed in a horizontal ball mill), weigh 2 g of the ground single mineral sample in each group and pour it into a 40 mL flotation tank, add a pH adjuster to adjust the slurry to pH = 8, add 35 mL of deionized water and then add the composite collector of this embodiment, add an appropriate amount of deionized water, stir for 3 min, add pinene alcohol (dosage is 10 g / t), stir for 3 min, start scraping, scrape for 3 min, the concentrate is scraped into the concentrate basin with the foam, and the tailings remain in the flotation tank. The concentrate and tailings are filtered and dried and weighed separately to calculate the recovery rate. Each group of experiments is carried out in three parallel groups, and the average value is taken. Figure 2 It is the recovery rate of each sulfide mineral in Example 1 at different dosages of composite collector.

[0051] like Figure 2 As shown in the figure, the composite reagent of this embodiment has the selective capture ability for chalcopyrite and galena in the lead-zinc-copper-iron sulfide ore when the slurry pH is 8. -5 mol / L, about 60 g / t), galena and chalcopyrite can be efficiently collected (recovery rate exceeds 95%), while the recovery rates of sphalerite and pyrite are both lower than 30%, and the recovery rate differences of lead-iron sulfide ore, lead-zinc sulfide ore, copper-iron sulfide ore, and copper-zinc sulfide ore are all greater than 65%, which proves that the composite collector of this embodiment has excellent flotation performance.

[0052] Example 2

[0053] In order to verify the effect of regulating the pH of the slurry on the flotation effect of the composite collector, high-purity galena, sphalerite, chalcopyrite and pyrite pure minerals (Table 1) were used. Figure 1 The single mineral flotation process shown in the figure uses the composite collector in this case to collect different sulfide minerals. The dosage of the composite collector is 1×10 -5 mol / L (about 60 g / t). Except for the different pulp pH, the flotation process parameters of each group of cases are the same. In this example, pineneol is added as a frother (the dosage is 10 g / t), and hydrochloric acid and sodium hydroxide are used as pH adjusters.

[0054] The composite collector of this embodiment: the compound of formula 1 ( ), the compound of formula 2 ( ), the compound of formula 3 ( ) and the compound of formula 4 ( ); The weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 5:1:2:2.

[0055] use Figure 1 The process shown in the figure is as follows: dry-grind pure mineral ore (particle size of 3 mm~0.5 mm) for 15 min (particle size after grinding is 0.074~0.038 mm, dry-grinded by horizontal ball mill), weigh 2 g of the ground single mineral sample in each group and pour it into a 40 mL flotation tank, add a pH adjuster to adjust the slurry to pH = 8, add 35 mL of deionized water and then add the composite collector of this embodiment, add an appropriate amount of deionized water, stir for 3 min, add pine alcohol (dosage is 10 g / t), stir for 3 min, start scraping, scrape for 3 min, the concentrate is scraped into the concentrate basin with the foam, and the tailings remain in the flotation tank. The concentrate and tailings are filtered and dried and weighed separately to calculate the recovery rate. Each group of experiments is carried out in three parallel groups and the average value is taken. Figure 2 It is the recovery rate of each sulfide mineral in Example 2 under different slurry pH conditions.

[0056] like Figure 3 As shown, the selectivity of the composite reagent of this embodiment under acidic conditions is much lower than that under neutral or alkaline conditions. When the sulfide ore to be selected contains chalcopyrite, the chalcopyrite is enriched in the flotation concentrate after flotation by the composite collector; when the sulfide ore to be selected contains pyrite, the pyrite is enriched in the flotation tailings after flotation by the composite collector; when the sulfide ore to be selected contains sphalerite, it is enriched in the flotation concentrate when the flotation pH is below 7.5; it is enriched in the flotation tailings when the flotation pH is greater than 7.9.

[0057] More specifically, when the pH of the ore pulp is 6-10, the composite collector of this embodiment can effectively separate lead-iron sulfide ore and copper-iron sulfide ore; when the pH of the ore pulp is 6-7, the composite collector of this embodiment can effectively separate zinc-iron sulfide ore; when the pH of the ore pulp is 8-10, the composite collector of this embodiment can effectively separate lead-zinc sulfide ore and copper-zinc sulfide ore. In the above cases, the recovery rate difference of lead-iron sulfide ore, lead-zinc sulfide ore, copper-iron sulfide ore, and copper-zinc sulfide ore is greater than 65%, which proves that the composite collector of this embodiment is widely applicable to systems under different pH conditions and maintains excellent flotation performance.

[0058] Example 3

[0059] In order to verify the effect of regulating the pH value of the slurry on the flotation effect of the composite collector on different sulfide ore mixtures, high-purity galena, sphalerite and pyrite pure mineral samples with a diameter of -0.074+0.038 mm were used to prepare three kinds of mixed ores in a 1:1:1 ratio (Table 1). Figure 1The mixed ore flotation process shown in the figure uses the composite collector in this case to collect the mixed ore. The dosage of the composite collector is 1×10 -5 mol / L (about 60 g / t), the pulp pH is 7 (Group A) or pH is 8 (Group B), the other flotation process parameters of each group of cases are the same, in this example, pineneol is added as a frother (the dosage is 10 g / t), and hydrochloric acid and sodium hydroxide are used as pH adjusters.

[0060] The composite collector of this embodiment: the compound of formula 1 ( ), the compound of formula 2 ( ), the compound of formula 3 ( ) and the compound of formula 4 ( ); The weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 5:1:2:2.

[0061] use Figure 1 The process shown in the figure is as follows: 2 g of the mixed ore sample is weighed in each group and poured into a 40 mL flotation tank, a pH adjuster is added to adjust the pulp to pH = 7 or 8, 35 mL of deionized water is added, and then the composite collector of this embodiment is added, and an appropriate amount of deionized water is added, stirred for 3 min, and pine alcohol (dosage is 10 g / t) is added, stirred for 3 min, and foaming is started. The foaming is scraped for 3 min, and the concentrate is scraped into the concentrate basin with the foam, and the tailings remain in the flotation tank. 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. Table 2 shows the recovery rate and grade of the mixed ore under different pulp pH conditions in Example 3.

[0062] ;

[0063] As shown in Table 2, when dealing with the complex sulfide ore mixed minerals of galena-sphalerite-pyrite, the composite collector of this embodiment still shows excellent flotation performance. When the pulp pH is 7, galena and sphalerite are both higher than 90%, the recovery rate of pyrite is only 27.6%, and the Pb grade is 38.4%, the Zn grade is 27.4%, and the Fe grade is only 5.8%. When the pulp pH is 8, galena is as high as 96.6%, and the recovery rates of sphalerite and pyrite are only 20.2% and 26.3%, respectively, while the Pb grade is 57.7%, the Zn grade is only 9.1%, and the Fe grade is only 8.3%.

[0064] Example 4

[0065] The effect of the present invention is further illustrated by taking an actual high-sulfur lead-zinc mine in Yunnan Province (element composition shown in Table 1) as an example. Figure 1The actual ore flotation process shown in the figure has the following specific steps: the actual ore is wet-milled by ball milling to make 80% of the ore particles less than 0.074 mm. 500 g of raw ore is ground (the grinding pH is the original ore pH (about 8 in this case), the particle size before grinding is 0.150~0.074 mm, and the particle size after grinding is 75~80% less than 0.074 mm). Figure 1 The flotation experiment was carried out in a 1.5 L flotation machine. The raw ore was wet-ground and poured into a 1.5 L flotation cell. A specified amount of composite flotation reagent was added. An appropriate amount of water was added. The pH adjuster was used to adjust the pulp to pH 7 (Group A) or pH 8 (Group B). The frother was 2 # The concentration of oil (10 g / t) and the concentration of composite collector were both 60 g / t. The mixture was aerated and stirred for 3 min. The scraper was turned on to automatically scrape the foam. Concentrates 1, 2, 3, and 4 were all coarse concentrate products. They were scraped to each concentrate basin along with the foam. The rougher tailings remained in the flotation tank. Each concentrate and tailings were weighed after filtration and drying. The metal grade of the total rougher concentrate (mixed rougher concentrates) and tailings was tested and the recovery rate was calculated. The experiment was repeated 3 times for each condition and the average value was taken. The results are shown in Table 3.

[0066] The composite collector of this embodiment: the compound of formula 1 ( ), the compound of formula 2 ( ), the compound of formula 3 ( ) and the compound of formula 4 ( ); The weight ratio of the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 is 6:1:2:1.

[0067] ;

[0068] As shown in Table 3, in the case of lead-zinc minerals, the composite collector of this embodiment still exhibits excellent flotation performance. When the pH of the slurry is 7, the recovery rates of galena and sphalerite are both higher than 90%, and the recovery rate of pyrite is only 25.8%. When the pH of the slurry is 8, the recovery rates of galena are as high as 92.5%, and the recovery rates of sphalerite and pyrite are only 27.2% and 24.8%, respectively. Through the flotation collector of the present invention and the regulation of pH, the selective separation of different purpose minerals is achieved.

[0069] Example 5

[0070] Compared with Example 4, the only difference is that Formula 3 is replaced by , replace equation 4 with , other operations and parameters are the same as those in Example 4. The test results are shown in Table 4.

[0071] ;

[0072] From the results of Example 5 and Example 4, it can be seen that the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in the composite collector of the present invention are substituted with preferred substituents (C 2 ~C 6 When the high sulfur lead-zinc ore is subjected to the flotation separation, the recovery rate and grade of pyrite in the rough concentrate are very low. 3 , R 4 C 3 ~C 6 When the alkyl group is substituted by an alkyl radical, better pH-controlled sorting selectivity can be obtained.

[0073] Example 6

[0074] Compared with Example 4, the only difference is that the weight ratio of the compounds of Formula 1, Formula 2, Formula 3 and Formula 4 is controlled to be 7:1:1:1, and the other operations are the same as those of Example 4. The test results are shown in Table 5.

[0075] ;

[0076] It can be seen from the results of Example 6 and Example 5 that when the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 in the composite collector of the present invention are compounded in a preferred ratio (5-7:1:1-2:1-2), the comprehensive flotation performance of the flotation agent can be effectively improved, and the grade of the lead (or zinc) rough concentrate can be improved while maintaining a good lead (or zinc) recovery rate.

[0077] Example 7

[0078] Compared with Example 4, the only difference is that the dosage of the composite collector and the frother is changed. The experimental groups are:

[0079] Group A: The dosage of the composite collector is 100 g / t, the dosage of the foaming agent is 5 g / t, and the rest is the same as in Example 5A;

[0080] Group B: The amount of the composite collector was 100 g / t, the amount of the foaming agent was 5 g / t, and the rest was the same as in Example 5B. The test results are shown in Table 6.

[0081] ;

[0082] It can be seen from the results of Example 7 and Example 4 that when the amount of the composite collector and the frother is limited within the required range of the present invention, excellent actual roughing flotation indexes of the ore can be obtained. At the same time, as the amount of the composite collector increases, the foaming performance of the composite collector is enhanced, and the amount of the frother can be further reduced.

[0083] Comparative Example 1

[0084] Compared with Example 4, the only difference is that the composition of the composite collector is changed. The experimental groups are:

[0085] Group A1: Formula 1 is missing, and the proportions of other remaining components and the total amount of collector are the same as those in Example 4A;

[0086] Group B1: Formula 1 is missing, and the proportions of other remaining components and the total amount of collector are the same as those in Example 4B;

[0087] Group A2: Formula 2 is missing, the weight ratio of Formula 1, Formula 2, Formula 3 and Formula 4 is 6:0:2:2, and the total amount of collector is the same as that of Example 4A;

[0088] Group B2: Formula 2 is missing, the weight ratio of Formula 1, Formula 2, Formula 3 and Formula 4 is 6:0:2:2, and the total amount of collector is the same as that of Example 4B;

[0089] Group A3: Formula 3 is missing, and the proportions of other remaining components and the total amount of collector are the same as those in Example 4A;

[0090] Group B3: Formula 3 is missing, and the proportions of other remaining components and the total amount of collector are the same as those in Example 4B;

[0091] Group A4: Formula 4 is missing, and the proportions of other remaining components and the total amount of collector are the same as those in Example 4A;

[0092] Group B4: Formula 4 is missing, and the proportions of other remaining components and the total amount of collector are the same as those in Example 4B;

[0093] Group A5: Formula 3 and Formula 4 are missing, the weight ratio of Formula 1, Formula 2, Formula 3 and Formula 4 is 9:1:0:0, and the total amount of collector is the same as that of Example 4A;

[0094] Group B5: Formula 3 and Formula 4 are missing, the weight ratio of Formula 1, Formula 2, Formula 3 and Formula 4 is 9:1:0:0, and the total amount of collector is the same as that of Example 4B;

[0095] Group A6: lacking Formula 2, Formula 3, and Formula 4, and the remaining components and the total amount of collector are the same as those in Example 4A;

[0096] Group B6: Formula 2, Formula 3, and Formula 4 are missing, and the remaining components and the total amount of collector are the same as those in Example 4B.

[0097] The results of each group are shown in Tables 7 and 8;

[0098] ;

[0099] ;

[0100] It can be seen from Example 4 and Comparative Example 1 that a better pH-sensitive sorting selectivity can be obtained by using a combination of collectors.

[0101] Comparative Example 2

[0102] Compared with Example 3, the only difference is that the weight ratio of Formula 1, Formula 2, Formula 3 and Formula 4 in the composite collector is controlled to be 1: 1: 1: 1, the total collector dosage and other parameters are the same as Example 3, and the flotation effect is shown in Table 9:

[0103] ;

[0104] It can be seen from Table 9 that by using the components and proportions described in the present invention, synergy can be achieved and better pH control adaptability and sorting selectivity can be obtained.

[0105] Comparative Example 3

[0106] Compared with Example 5, the only difference is that in the composite collector, As formula 1; using As Formula 2, other operations and parameters are shown in Example 5, and the results are shown in Table 10:

[0107] ;

[0108] From the above embodiments and comparative examples, it can be seen that when the compounds of Formula 1, Formula 2, Formula 3 and Formula 4 in the composite collector of the present invention are compounded in a preferred ratio (5-7:1:1-2:1-2), the comprehensive flotation performance of the flotation agent can be effectively improved, and the grade of the lead (or zinc) rough concentrate can be improved while maintaining a good lead (or zinc) recovery rate. If the compounding ratio exceeds the specified ratio range (such as a ratio of 1:1:1:1, 1:0:0:0, 6:0:2:2, 9:1:0:0), the flotation performance of the composite collector is significantly deteriorated, and the recovery rate and grade of the rough concentrate are significantly reduced.

[0109] The compounds of Formula 1, Formula 2, Formula 3 and Formula 4 in the composite collector of the present invention are substituted by preferred substituents (C 2 ~C 6 When the alkane or aromatic hydrocarbon is present, the high-sulfur lead-zinc ore can obtain excellent flotation separation effect, and the recovery rate and grade of pyrite in the rough concentrate are very low. However, when the substituent structure of the compound of Formula 1, Formula 2, Formula 3, and Formula 4 in the composite collector of the present invention exceeds the range described in the present invention (such as methyl), the recovery rate and grade of the obtained rough concentrate are significantly reduced, that is, the flotation index becomes worse.

[0110] The composite collector of the present invention can selectively capture galena and sphalerite in high-sulfur lead-zinc ore under neutral conditions (pH = 7), but not pyrite; the composite collector of the present invention can selectively capture galena in high-sulfur lead-zinc ore under weakly alkaline conditions (pH = 8), but not sphalerite and pyrite.

[0111] The above results show that the composite collector of the present invention can achieve green and efficient separation and enrichment of complex sulfide minerals, and the flotation indicators (recovery rate and grade) of complex sulfide ores can be further improved by regulating the substituents in the compounds of Formula 1, Formula 2, Formula 3, and Formula 4 described in the present invention, the compounding ratio of each compound, or the pH value of the slurry.

[0112] In the present invention, the pH regulation of the flotation pulp is also the key to synergistically improving the flotation index. When the pH range of the pulp is 6-10, it is suitable for the flotation separation of lead-iron and copper-iron sulfide ores, when the pH range is 6-7, it is suitable for the flotation separation of zinc-iron sulfide ores, and when the pH range is 8-10, it is suitable for the flotation separation of lead-zinc sulfide ores; preferably, when the pH range of the pulp is 7-9, it is suitable for the flotation separation of lead-iron and copper-iron sulfide ores, when the pH is 7, it is suitable for the flotation separation of zinc-iron sulfide ores, and when the pH is 8-9, it is suitable for the flotation separation of lead-zinc sulfide ores; further preferably, when the pH range of the pulp is 7-8, it is suitable for the flotation separation of lead-iron and copper-iron sulfide ores, when the pH is 7, it is suitable for the flotation separation of zinc-iron sulfide ores, and when the pH is 8, it is suitable for the flotation separation of lead-zinc and copper-zinc sulfide ores. The present invention shows that the use of the preferred pulp pH conditions can unexpectedly obtain stronger capture capacity and higher selectivity.

Claims

1. A composite collector for flotation of sulfide ores, 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 2-7:1-2:1-3:1-3; Formula 1 Formula 2 Formula 3 Formula 4 The R1-R4 are independently alkyl, aryl, heteroaryl, olefin, alkynyl, substituted alkyl or substituted phenyl with 2 to 8 carbon atoms; the M is H, NH4, Na or K; The sulfide ore comprises at least one of galena, chalcopyrite and sphalerite.

2. The composite collector for flotation of sulfide ores according to claim 1, characterized in that: The R1 and R2 are independently phenyl or substituted phenyl, and the substituted phenyl is a phenyl with at least one substituent selected from alkyl, alkoxy and halogen; The R3 and R4 are independently C3~C6 alkyl groups.

3. The composite collector for flotation of sulfide ore according to claim 1 or 2, characterized in that: 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 5-7:1:1-2:1-2.

4. A method for flotation of sulfide ore, comprising mixing the sulfide ore to be selected with a flotation agent containing a collector, flotation, and collecting the flotation concentrate and flotation tailings, characterized in that: The collector is the composite collector according to any one of claims 1 to 3; The sulfide ore comprises at least one of galena, chalcopyrite and sphalerite.

5. The method for flotation of sulfide ore according to claim 4, characterized in that: When the sulfide ore to be selected contains galena, the galena is enriched in the flotation concentrate after flotation by the composite collector; When the sulfide ore to be selected contains chalcopyrite, the chalcopyrite is enriched in the flotation concentrate after flotation by the composite collector; When sphalerite is contained in the sulfide ore to be selected, it is enriched in the flotation concentrate when the flotation pH is below 7.5; it is enriched in the flotation tailings when the flotation pH is greater than 7.

9.

6. The method for flotation of sulfide ore according to claim 5, characterized in that: The sulfide ore to be selected is mineral A, which includes mineral A1 and mineral A2, wherein mineral A1 includes at least one of galena and chalcopyrite; and mineral A2 includes pyrite; Mineral A is floated at a pH of 5-10, wherein mineral A1 is enriched in the flotation concentrate and mineral A2 is enriched in the flotation tailings.

7. The method for flotation of sulfide ore according to claim 5, characterized in that: The sulfide ore to be selected is mineral B, which includes mineral B1 and mineral B2, wherein mineral B1 includes sphalerite; and mineral B2 includes pyrite; When the pH of flotation is 5-7, mineral B1 is enriched in the flotation concentrate and mineral B2 is enriched in the flotation tailings.

8. The method for flotation of sulfide ore according to claim 7, characterized in that: The mineral B1 further includes a mineral B1a, wherein the mineral B1a includes at least one of chalcopyrite and galena; When the pH of flotation is 5-7, mineral B1 is enriched in the flotation concentrate, and mineral B2 is enriched in the flotation tailings; When the pH value of flotation is 8-10, mineral B1a in mineral B1 is enriched in the flotation concentrate, and sphalerite and mineral B2 in mineral B1 are enriched in the flotation tailings.

9. The method for flotation of sulfide ore according to claim 5, characterized in that: The sulfide ore to be selected is mineral C, which includes mineral C1 and mineral C2, wherein the mineral C1 includes at least one of chalcopyrite and galena, and the mineral C2 includes sphalerite; under the flotation condition of pH 8-10, mineral C1 is enriched in the flotation concentrate, and mineral C2 is enriched in the flotation tailings.

10. The method for flotation of sulfide ore according to any one of claims 5 to 9, characterized in that: The dosage of composite collector in flotation process is more than 10 g / t; A frother is also added to the flotation reagent, with the dosage not exceeding 50 g / t.

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