High-sulfur complex lead-zinc polymetallic ore flotation collector, and preparation method and application thereof

Abstract

This invention provides a flotation collector for high-sulfur complex lead-zinc polymetallic ores, its preparation method, and its application. The collector is N,N'-dibromophenyl dithioaminophosphate, prepared by reacting o-bromoaniline with phosphorus pentasulfide in toluene. This collector exhibits strong collecting ability, good selectivity, non-sticky flotation froth, low middlings recycling volume, and strong adaptability for lead sulfide minerals. It is convenient to use, requires a small dosage, and simplifies the flotation process, reducing flotation costs and environmental impact, thus achieving better flotation separation of high-sulfur lead-zinc ores. Furthermore, this collector can also recover various associated gold and silver minerals in high-sulfur complex lead-zinc polymetallic ores, demonstrating broad applicability and strong adaptability, especially for fine-grained associated gold and silver minerals with a particle size less than 37 μm, exhibiting strong collecting ability and good selectivity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral processing, in particular to a high-sulfur complex lead-zinc polymetallic ore flotation collector and a preparation method and application thereof. BACKGROUND

[0002] China is rich in lead-zinc ore resources, which are characterized by wide distribution and concentration, complex ore types, more associated valuable components, less lean ore and more rich ore. Although the lead-zinc ore resources reserves are relatively abundant, due to continuous mining in recent years, the lead-zinc ore resources that are easy to mine, have complete structure and good floatability are decreasing year by year, and the present situation is "poor, fine and miscellaneous", which brings many challenges to beneficiation technology. As a common type of lead-zinc ore, high-sulfur lead-zinc ore has a high sulfur content in the raw ore, and the main iron sulfide ore is pyrite. Due to the unevenness of the surface structure and the difference of the lattice defects of pyrite under different ore-forming conditions, the activation of the inevitable ions and the galvani effect, the floatability of pyrite changes greatly, which leads to the difficulty in controlling the separation of lead-sulfur and zinc-sulfur.

[0003] In view of the problems of high-sulfur lead-zinc ore, the existing technology generally adopts high-alkali method to suppress sulfur, and for the separation of high-sulfur polymetallic sulfide ore, the following problems often exist due to the large amount of lime used: ① high pH of the ore pulp, difficult to recycle the beneficiation wastewater; ② easy to be blocked by calcium in the ore pulp conveying pipeline and filter; ③ low recovery rate of associated gold and silver and other precious metals due to high-alkali environment, and difficult to activate subsequent metal minerals, high cost of reagent; ④ sticky flotation froth, serious entrainment, low concentrate grade, difficult to produce and control, and large fluctuation of indicators.

[0004] In summary, it is urgent to develop a high-efficiency selective collector and its application to solve the problems of low recovery rate of associated gold and silver, pipeline calcium blocking and poor adaptability of reagents to associated gold and silver minerals caused by high-alkali sulfur suppression. SUMMARY

[0005] The present application provides a high-sulfur complex lead-zinc polymetallic ore flotation collector and its application, which aims to solve the problems of low recovery rate of associated gold and silver caused by adding lime to suppress sulfur and arsenic in the conventional process, sticky flotation froth, low concentrate grade, and easy calcium blocking in the ore pulp conveying pipeline and filter.

[0006] In order to achieve the above object, the embodiment of the present application provides a high-sulfur complex lead-zinc polymetallic ore flotation collector and a preparation method and application thereof, the collector is N,N'-dibromophenyl dithio phosphoramide, the preparation method is that o-bromoaniline and phosphorus pentasulfide are prepared according to a molar ratio of 4:1-8:1, the amount of solvent toluene is 12-18 times of the mass of phosphorus pentasulfide, the reaction is carried out at a reaction temperature of 30-50 DEG C, and the collector is prepared after 1h-3h of reaction. The collector has the characteristics of strong collecting capacity for lead sulfide minerals, good selectivity, non-stick of flotation foam, small middling circulation, strong adaptability and the like. The collector is convenient to use, the amount is small, the types of flotation reagents are simple, the flotation cost and the harm to the environment are reduced, and the flotation separation of high-sulfur lead-zinc ore is better realized.

[0007] The embodiment of the present application provides a high-sulfur complex lead-zinc polymetallic ore flotation collector, the lead-zinc sulfur is closely associated in the high-sulfur complex lead-zinc polymetallic ore, and the sulfur content is greater than 15%, the collector is N,N'-dibromophenyl dithio phosphoramide, and the chemical formula is as follows:

[0008]

[0009] The embodiment of the present application also provides a preparation method of the high-sulfur complex lead-zinc polymetallic ore flotation collector, the preparation method is that o-bromoaniline and phosphorus pentasulfide are dissolved in toluene and reacted.

[0010] As further preferred, the molar ratio of the o-bromoaniline to the phosphorus pentasulfide is 4:1-8:1, and the amount of toluene is 12-18 times of the mass of the phosphorus pentasulfide.

[0011] As further preferred, the reaction temperature is 30-50 DEG C, and the reaction time is 1h-3h.

[0012] Based on the general concept of the application, the present application also provides the application of the high-sulfur complex lead-zinc polymetallic ore flotation collector in high-sulfur complex lead-zinc polymetallic ore dressing, and the application comprises the following steps:

[0013] S1, after ore samples are coarsely crushed, medium crushed and finely crushed to-3mm, the finely crushed ore samples are obtained, wet ball milling is carried out, and the raw ore slurry is obtained;

[0014] S2, after the zinc mineral inhibitor and the collector are sequentially added into the raw ore slurry obtained in step S1, full slurry stirring is carried out, and lead flotation roughing is carried out, lead rough concentrate and lead rough tailings are obtained;

[0015] S3, zinc mineral inhibitor and collector are added into the lead roughing tailings obtained in step S2 in turn, and after lead scavenging operation, the scavenging tailings are lead tailings, and the lead tailings enter zinc selection operation, and the scavenging middlings return to the previous operation in turn;

[0016] S4, zinc mineral inhibitor is added into the lead rough concentrate obtained in step S2, and after lead concentrate cleaning operation, lead concentrate is obtained, and the cleaning middlings return to the previous operation in turn.

[0017] As a further optimization, the ground ore sample is ground to -0.074 mm accounting for 60% to 80%; the mass fraction of the ore slurry is 25% to 30%.

[0018] As a further optimization, the zinc mineral inhibitor is at least one of sodium sulfite and zinc sulfate.

[0019] As a further optimization, in step S2: the zinc mineral inhibitor is sodium sulfite and zinc sulfate; the amount of sodium sulfite used is 150 to 250 g / t of ore, and the amount of zinc sulfate used is 500 to 1200 g / t of ore; the amount of collector used is 40 to 60 g / t of ore; and the flotation time of the roughing operation is 2 to 4 min.

[0020] As a further optimization, in step S3: the scavenging operation is 1 to 2 times; in the first scavenging operation: the zinc mineral inhibitor is zinc sulfate, the amount used is 200 to 400 g / t of ore, the amount of collector used is 10 to 20 g / t of ore, and the flotation time is 2 to 3 min; in the second scavenging operation: the amount of collector used is 10 to 20 g / t of ore, and the flotation time is 1.5 to 2.5 min.

[0021] As a further optimization, in step S4: the cleaning operation is 2 to 3 times; in the first cleaning operation: the zinc mineral inhibitor is zinc sulfate, the amount used is 150 to 300 g / t of ore, and the flotation time is 2 to 4 min; in the second cleaning operation: the zinc mineral inhibitor is zinc sulfate, the amount used is 50 to 150 g / t of ore, and the flotation time is 1.5 to 3 min; in the third cleaning operation: the zinc mineral inhibitor is zinc sulfate, the amount used is 50 to 150 g / t of ore, and the flotation time is 1.5 to 3 min.

[0022] The associated gold and silver resources in lead-zinc sulfide ore are an important part of the gold and silver resources in China, and the associated gold reserves in non-ferrous metal sulfide ore resources account for more than 27% of the total gold reserves, and the associated silver reserves account for more than 90% of the total silver reserves in China. Strengthening the recovery of associated gold and silver, especially the recovery of associated gold and silver in lead concentrate, is of great significance to improve the comprehensive utilization rate of valuable elements in lead-zinc sulfide ore, improve the comprehensive economic value of the mine, and meet the demand of the national economy for gold and silver.

[0023] The principle of the flotation method of the present application is as follows:

[0024] The structure and performance of the non-polar group of the flotation collector determine the degree of hydrophobicity of the mineral surface, affect the solid affinity and selectivity of the collector, and affect the water solubility of the reagent and the solubility of the collector-metal salt. The length and structural characteristics of the non-polar group can indirectly affect the solid affinity of the polar group through d-Π, Π electron-induced effect, conjugation effect and space effect.

[0025] The aromatic ring phenyl has the structural characteristics of its conjugated large Π bond, which determines that the flotation reagent has a large polarity, so it has a strong hydrophilicity and a good solubility and dispersion ability. At the same time, the phenyl generally has a large steric hindrance effect, which can improve the selectivity of the reagent.

[0026] The electronegativity of the halogen bromine atom is larger than that of carbon, which increases the polarity of the non-polar group in the non-polar group, and can improve the solubility and dispersion ability of the reagent. At the same time, the hydrocarbon group containing bromine atom has a large electronic induction effect, which affects the coordination ability of the bonding atom of the reagent, and is the direction of improving the reagent modification.

[0027] The flotation collector provided by the present application belongs to the derivative of black medicine collector, and has good collecting and foaming performance of black medicine collector. The collector provided by the present application increases the polarity of the non-polar group by introducing phenyl and bromine atom in the non-polar group, and improves the solubility and dispersion ability and selectivity of the reagent.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] (1) The application adopts "N, N'-dibromophenyl dithio phosphoramide" as a flotation collector, cooperates with a specific flotation process, and applies the beneficiation method for recovering lead minerals in high-sulfur complex lead-zinc polymetallic ore, which effectively avoids the problems in the conventional process, such as low recovery rate of associated gold and silver, sticky flotation froth, low concentrate grade, and easy calcium deposition in the pipeline and filter of the ore slurry, caused by adding lime to suppress sulfur and arsenic. The collector is convenient to use and has small dosage, which reduces the flotation cost and the harm to the environment. The application can also recover different types of associated gold and silver minerals in high-sulfur complex lead-zinc polymetallic ore, has certain universality, strong adaptability of reagent, especially strong collecting ability and good selectivity for fine-grained associated gold and silver minerals with a particle size of less than 37 μm, and effectively solves the poor adaptability of reagents for recovering associated gold and silver minerals in the prior art.

[0030] (2) The collector of the application can not only effectively recover lead, gold and silver minerals, but also reduce the floating of zinc and sulfur minerals without adding lime, avoid the inhibition of gold and silver minerals by lime, achieve the goal of further improving the recovery rate of associated gold and silver in lead concentrate, reduce the dosage of reagent, reduce the flotation cost, and make the flotation froth clean and the flotation process more green and environmentally friendly. It is a better "low-alkali and calcium-free" beneficiation process.

[0031] (3) The collector of the application has a wide source of raw materials and a green and environmentally-friendly preparation process. The collector has better collecting ability and selectivity for lead sulfide minerals than ethyl xanthate and ammonium butyl dithiophosphate, has good universality for this type of ore, especially strong collecting ability for associated gold and silver and other precious metals in the ore. The flotation process does not need to add a foaming agent, the flotation froth is not sticky, and the recycling amount of middlings is small. BRIEF DESCRIPTION OF DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without creative labor.

[0033] Figure 1 is a process flow diagram of the flotation collector for high-sulfur complex lead-zinc polymetallic ore in embodiment 1 applied to the flotation recovery of lead minerals in a certain gold and silver containing lead-zinc polymetallic ore in Anhui;

[0034] Figure 2 is a process flow diagram of the collector in comparative example 1 applied to the flotation recovery of lead minerals in a certain gold and silver containing lead-zinc polymetallic ore in Anhui;

[0035] Figure 3 Figure 1 is a process flow diagram of the application of the high-sulfur complex lead-zinc polymetallic ore flotation collector of embodiment 1 to the flotation recovery of lead minerals from a certain complex lead-zinc polymetallic ore in Jiangsu. DETAILED DESCRIPTION

[0036] To make the technical problems, technical solutions and advantages of the present application clearer, specific embodiments will be described in detail below with reference to the accompanying drawings.

[0037] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present application. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present application can be purchased on the market or can be prepared by existing methods.

[0038] The present application provides a high-sulfur complex lead-zinc polymetallic ore flotation collector, as well as a preparation method and application thereof, aiming at the existing problems.

[0039] Embodiment 1

[0040] A preparation method of a high-sulfur complex lead-zinc polymetallic ore flotation collector, in which the purity of o-bromoaniline and phosphorus pentasulfide is 99%, o-bromoaniline and phosphorus pentasulfide are mixed according to a molar ratio of 6:1, then dissolved in toluene, the amount of toluene solvent is 15 times the mass of phosphorus pentasulfide, the reaction is carried out at a reaction temperature of 30℃ for 2h, and the reaction mixture is washed and vacuum dried to obtain N,N'-dibromophenyl dithio phosphoramic acid with an analytical purity of 97.2%.

[0041] Embodiment 2

[0042] A preparation method of a high-sulfur complex lead-zinc polymetallic ore flotation collector, in which the purity of o-bromoaniline and phosphorus pentasulfide is 99%, o-bromoaniline and phosphorus pentasulfide are mixed according to a molar ratio of 8:1, then dissolved in toluene, the amount of toluene solvent is 16 times the mass of phosphorus pentasulfide, the reaction is carried out at a reaction temperature of 40℃ for 3h, and the reaction mixture is washed and vacuum dried to obtain N,N'-dibromophenyl dithio phosphoramic acid with an analytical purity of 98.6%.

[0043] Application Example 1

[0044] The main valuable elements of the raw ore of a certain gold-silver-lead-zinc polymetallic ore in Anhui are Pb and Zn with contents of 3.82% and 6.47% respectively, and the associated noble metals are Au and Ag with contents of 4.38 g / t and 136.66 g / t respectively, and the content of S is 17%; both lead and zinc are mainly in the form of sulfide ore, in which the content of lead sulfide is 93.46% and the content of zinc sulfide is 98.30%. According to the process mineralogy analysis, the main metallic minerals in the raw ore are pyrite, sphalerite and galena; the secondary metallic minerals are pyrrhotite, and trace amounts of arsenopyrite, cerussite and magnetite; the non-metallic minerals are mainly dolomite, calcite and quartz; and there are small amounts of kaolinite, clay, chlorite and feldspar. The lead and zinc are closely associated with sulfur, and the galena is closely related to sphalerite, pyrite and pyrrhotite. The galena is often intergrown with sphalerite and pyrite, and there are many adjacent minerals, which is not conducive to the dissociation of galena; most of the sphalerite is metasomatic pyrite, and the sphalerite often contains droplet-shaped, linear and punctate pyrite and galena (particle size <5 microns) inside, which leads to the difficulty in improving the grade of sphalerite.

[0045] The collector prepared in Example 1 is used for the flotation of a certain gold-silver-lead-zinc polymetallic ore in Anhui, and the flotation process flow according to the application comprises the following steps: Figure 1

[0046] (1) The silver-lead-zinc polymetallic ore raw ore is coarsely crushed, medium crushed and finely crushed to-3 mm to obtain a finely crushed ore sample to be treated. The finely crushed ore sample is ground, and the content of the ground ore sample with a particle size of-0.074 mm is 62.46%. After grinding, the ore slurry is prepared, and the mass fraction of the ore slurry is 26%.

[0047] (2) According to the amount of the raw ore, 200 g / t of sodium sulfite and 1000 g / t of zinc sulfate are added to the ore slurry as zinc mineral combination inhibitors, and stirred for 3 min; then 60 g / t of the collector of the application is added, and stirred for 2 min; the flotation time is controlled to be 2.5 min to obtain a lead rough concentrate and a lead rough tailing.

[0048] (3) According to the amount of the raw ore, the lead rough tailing is subjected to two times of scavenging. In the first scavenging operation, 300 g / t of zinc mineral inhibitor zinc sulfate is added, stirred for 2 min, and then 10 g / t of the collector of the application is added, stirred for 2 min, and then subjected to flotation for 2 min; in the second scavenging operation, 10 g / t of the collector of the application is added, stirred for 2 min, and then subjected to flotation for 1.5 min. The scavenging tailing is a lead tailing, which is subjected to zinc selection operation, and the scavenging middling is sequentially returned to the previous flotation operation.

[0049] ​(4) The lead concentrate is subjected to three cleaning processes. In the first cleaning process, 200 g / t of zinc sulfate, a zinc mineral inhibitor, is added, stirred for 3 minutes, and then floated for 3 minutes. In the second cleaning process, 100 g / t of zinc sulfate, a zinc mineral inhibitor, is added, stirred for 3 minutes, and then floated for 2 minutes. The third cleaning process is a blank cleaning process with a floatation time of 1.5 minutes. The middlings from the cleaning process are returned to the previous stage of flotation. After three cleaning processes, the final lead concentrate product is obtained.

[0050] Comparative Example 1

[0051] according to Figure 2 For processing the polymetallic ore containing gold, silver, lead, and zinc in Application Example 1, the roughing flotation steps and parameters are the same as in Application Example 1. The only difference is that the collectors in this comparative example are butyl ammonium black, ethyl xanthate, and ethyl thiocyanate + butyl ammonium black. The amount of collectors used in Application Example 1 is the same as in Comparative Example 1. Comparative Example 1 only performed roughing and did not perform scavenging and cleaning.

[0052] The dosage of each collector in Comparative Example 1 is shown in Table 1. Application Example 1 uses the collector obtained in Example 1 of this invention, and Comparative Example 1 uses the same collector as Comparative Example 1. Figure 2 The experimental results obtained from only rough selection in the process flow are shown in Table 2. Application Example 1 uses the collector obtained in Example 1 of this invention according to... Figure 1 The closed-circuit test results obtained from the process flow are shown in Table 3.

[0053] Table 1 shows the dosage of each collector in Comparative Example 1.

[0054] Collector type Dosage (g / t raw ore) Ethyl xanthate 60 Butyl amine black 60 Ethyl thiourea + butyl amine black 45+30

[0055] Table 2 Comparison of Experimental Results (%)

[0056]

[0057]

[0058] From the results of Table 2, in Comparative Example 1, when using butyl ammonium black medicine as a collector, the amount of foam is large during the flotation process, and a large amount of slime is entrained to cause the grade of the rough concentrate to be low and the zinc mutual content to be high. The selectivity of ethyl xanthate as a collector is poor, the rough concentrate contains high sulfur and has low grade. The selectivity of the combined collector of ethyl thionocarbamate + butyl ammonium black medicine is better than that of ethyl xanthate and butyl ammonium black medicine, but the collecting ability is weak. After using the collector of the present application, under the same conditions, compared with the other three collectors, the collector has better selectivity and good collecting performance, the flotation foam is clean, the grade of the obtained rough concentrate is high, the mutual content is low, the recovery rate is high, and the amount of the collector is reduced by 15 g / t compared with the use of ethyl thionocarbamate + butyl ammonium black medicine. The collector provided by the present application has the characteristics of strong collecting ability and good selectivity for lead sulfide minerals, small amount of use, and low flotation cost, and has a wide industrial application prospect for high-sulfur complex lead-zinc polymetallic ore containing associated gold and silver.

[0059] Table 3 Application Example 1 closed-circuit test results (%)

[0060]

[0061] Note: * unit is g / t.

[0062] From the results of Table 3, in Application Example 1, the collector prepared by the present application is used according to the process flow of Figure 1 , under the condition that the grinding fineness is 62.46% -0.074mm, the combination of sodium sulfite and zinc sulfate is used as a zinc mineral inhibitor, and through one rough three concentrates and two scans, a lead concentrate containing 60.61% lead, 3.46% zinc, 32.80 g / t gold, 1608.85 g / t silver, a lead recovery rate of 90.37%, a gold recovery rate in lead concentrate of 42.21%, and a silver recovery rate of 67.22% can be obtained. The process flow of the lead production site, the type and amount of zinc mineral inhibitor are the same as those of Application Example 1, and the difference is that the collector for the lead production site is ethyl xanthate, the total amount of ethyl xanthate for the lead production site is 100 g / t, 2000 g / t of lime is added to the rough selection of the lead production site, the lead concentrate of the lead production site contains 59.52% lead, 4.95% zinc, 30.30 g / t gold, and 1565.66 g / t silver, the lead recovery rate is 85.04%, the zinc recovery rate is 4.15%, the gold recovery rate in the lead concentrate is 37.45%, and the silver recovery rate is 62.58%. Under the same conditions, by comparing the production site indicators with the closed-circuit test results of Application Example 1, it can be seen that the collector prepared by the present application has improved the grade of lead in the lead concentrate, the lead recovery rate is increased by 5.33%, the gold recovery rate in the lead concentrate is increased by 4.76%, the silver recovery rate is increased by 4.64%, and the loss rate of zinc in the lead concentrate is effectively reduced.

[0063] Application Example 2

[0064] The content of Pb and Zn in the raw ore of a complex lead-zinc polymetallic ore in Jiangsu is 1.71% and 3.52% respectively, the content of cobalt in the ore is only 0.022%, the content of precious metals gold and silver is low, the content of gold is less than 1 g / t, the content of silver is 8.5 g / t, and the content of S is 18.5%. Both lead and zinc are mainly in the form of sulfide ore, the proportion of lead in lead sulfide is 88.24%, the proportion of lead in lead oxide is 7.84%, and the proportion of lead in lead ferrite and other forms is 3.92%. The proportion of zinc in zinc sulfide is 96.61%, the proportion of zinc in zinc sulfate is 0.23%, the proportion of zinc in zinc iron spinel is 0.94%, and the proportion of zinc in zinc oxide ore is 2.22%. According to the process mineralogy analysis, the main metallic minerals in the ore are galena and sphalerite, followed by pyrite, jamesite, hematite, cerussite, and antimony. The main gangue minerals are mica, feldspar, quartz, chlorite, and calcite. The metallic minerals are mainly sphalerite, with a small amount of pyrite and galena. Lead and zinc are closely associated, and galena and sphalerite are mutually wrapped. Galena is irregularly or finely granular wrapped in sphalerite, which is not conducive to the separation of lead and zinc. The particle size of galena is medium-fine, and part of it is less than 20 microns, which is micro-fine or fine vein in sphalerite and gangue. This part of galena will be difficult to completely dissociate, affecting the recovery of lead minerals. The oxidation rate of lead in the ore is about 12%, and the existence of oxidized lead minerals will weaken the recovery rate of lead. Sphalerite is closely associated with galena and chalcopyrite, and it is common to see sphalerite wrapped in fine-grained galena and gangue, which is not conducive to the complete dissociation of sphalerite. The particle size of sphalerite is relatively coarse, mainly in the range of 0.07-1.0 mm, which is conducive to the recovery of mineral processing; but part of the sphalerite is finely granular and embedded in the interstitial space of gangue minerals, which is difficult to dissociate. Galena is closely related to sphalerite, pyrite, and chalcopyrite, and galena is often intergrown with sphalerite and pyrite, with many adjacent minerals, which is not conducive to the dissociation of galena. Most of the sphalerite is metasomatic pyrite, and sphalerite often wraps in drop-shaped, linear, and point-shaped pyrite and galena (particle size <5 microns), which makes it difficult to improve the grade of sphalerite.

[0065] The collector prepared in Example 2 was used for the flotation of a complex lead-zinc polymetallic ore in Jiangsu, and the flotation process flow according to Figure 3 includes the following steps:

[0066] (1) The complex lead-zinc polymetallic ore raw ore was coarsely crushed, medium crushed, and finely crushed to-3 mm to obtain a finely crushed ore sample for treatment. The finely crushed ore sample was ground, and the content of-0.074 mm in the flotation sample was 72.35%. After grinding, the slurry was prepared, and the mass fraction of the slurry was 26%.

[0067] (2) per ton of raw ore, zinc sulfate zinc mineral inhibitor is added into the slurry in turn, the amount of zinc sulfate used is 500 g / t, stirring for 3 min; then adding 40 g / t of the collector of the application, stirring for 2 min; controlling the flotation time to be 2 min, to obtain lead rough concentrate and lead roughing tailings.

[0068] (3) per ton of raw ore, the lead roughing tailings are subjected to one scavenging operation, the scavenging operation adding 10 g / t of the collector prepared in Example 2 of the application, stirring for 2 min and then floating, the floating time being 2 min. The scavenging tailings are lead tailings, and the lead tailings enter the zinc selection operation, and the scavenging middlings are sequentially returned to the upper stage of the floating operation.

[0069] (4) the lead rough concentrate is subjected to three cleaning operations, the first cleaning operation adding zinc mineral inhibitor zinc sulfate 200 g / t, stirring for 3 min and then floating, the floating time being 2 min; the second cleaning operation adding zinc mineral inhibitor zinc sulfate 100 g / t, stirring for 3 min and then floating, the floating time being 1.5 min; the third cleaning operation adding zinc mineral inhibitor zinc sulfate 50 g / t, stirring for 3 min and then floating, the floating time being 1.5 min. The cleaning middlings are sequentially returned to the upper stage of the floating operation, and after the three cleaning operations, the final lead concentrate product is obtained.

[0070] The closed-circuit test results obtained by using the collector prepared in Example 2 of the application according to the process flow of Figure 3 are shown in Table 4.

[0071] Table 4 Closed-circuit test results of application example 2 (%)

[0072]

[0073] As can be seen from the results in Table 4, in application example 2, the collector prepared in Example 2 of the application is used according to the process flow of Figure 3 , under the condition that the grinding fineness is 72.35% -0.074 mm, zinc sulfate is used as the zinc mineral inhibitor, and one roughing, three cleaning and one scavenging can obtain lead concentrate containing 58.25% lead and 2.26% zinc, with a lead recovery rate of 88.56% and a zinc recovery rate of 1.68%. The process flow of the lead selection operation, the type and amount of the zinc mineral inhibitor in the production site are the same as those in application example 2, and the difference is that the collector for the lead selection operation in the production site is ethylthiuram, and the total amount of ethylthiuram used in the lead selection operation is 60 g / t. The lead concentrate in the production site contains 55.06% lead and 3.96% zinc, with a lead recovery rate of 79.58% and a zinc recovery rate of 2.73%. Under the same conditions, by comparing the production site indicators with the closed-circuit test results of application example 2, it can be seen that the use of the collector prepared in Example 2 of the application can improve the grade of lead in the lead concentrate, increase the lead recovery rate by 8.98%, and effectively reduce the loss rate of zinc in the lead concentrate.

[0074] In summary, the application adopts "N, N'-dibromophenyl dithio phosphoric acid" as a flotation collector, cooperates with a specific flotation process, and applies the beneficiation method for recovering lead minerals in high-sulfur complex lead-zinc polymetallic ore, which effectively avoids the problems such as low recovery rate of associated gold and silver, sticky flotation foam, low concentrate grade, and easy calcium plugging of slurry conveying pipeline and filter in the conventional process by adding lime to suppress sulfur and arsenic. The collector is convenient to use, has small dosage, reduces the flotation cost and the harm to the environment. The application can also recover different types of associated gold and silver minerals in high-sulfur complex lead-zinc polymetallic ore, has certain universality, has strong adaptability of reagent, especially has strong collecting ability and good selectivity for fine-grained associated gold and silver minerals with a particle size of less than 37 μm, and effectively solves the problem of poor adaptability of reagent for recovering associated gold and silver minerals in the prior art.

[0075] The above is the preferred embodiment of the application, and it should be pointed out that for ordinary skilled persons in the art, some improvements and refinements can be made without departing from the principles of the application, and these improvements and refinements should also be considered as the protection scope of the application.

Claims

1. A flotation collector for high-sulfur complex lead-zinc polymetallic ores, wherein the lead, zinc, and sulfur are closely associated, and the sulfur content is greater than 15%, characterized in that... The collector is N,N'-dibromophenyldithioaminophosphate, and its chemical formula is as follows: ； The preparation method of the flotation collector for high-sulfur complex lead-zinc polymetallic ores is as follows: o-bromoaniline and phosphorus pentasulfide are dissolved in toluene and reacted; wherein, the molar ratio of o-bromoaniline to phosphorus pentasulfide is 4:1 to 8:1, and the amount of toluene is 12 to 18 times the mass of phosphorus pentasulfide; the reaction temperature is 30 to 50°C, and the reaction time is 1 to 3 hours.

2. The preparation method of the flotation collector for high-sulfur complex lead-zinc polymetallic ores as described in claim 1, characterized in that, The preparation method involves dissolving o-bromoaniline and phosphorus pentasulfide in toluene and reacting them.

3. The preparation method according to claim 2, characterized in that, The molar ratio of o-bromoaniline to phosphorus pentasulfide is 4:1 to 8:1, and the amount of toluene used is 12 to 18 times the mass of phosphorus pentasulfide.

4. The preparation method according to claim 3, characterized in that, The reaction temperature is 30~50℃, and the reaction time is 1h~3h.

5. The application of the flotation collector for high-sulfur complex lead-zinc polymetallic ores as described in claim 1 or the flotation collector for high-sulfur complex lead-zinc polymetallic ores prepared by any one of claims 2 to 4 in the beneficiation of high-sulfur complex lead-zinc polymetallic ores, characterized in that, The application includes the following steps: S1. Take an ore sample and crush it into coarse, medium and fine ore to -3mm to obtain a fine crushed ore sample. Then, perform wet ball milling to obtain raw ore slurry. S2. Zinc mineral inhibitor and collector are added sequentially to the raw ore slurry obtained in step S1. After thorough slurry preparation and stirring, lead flotation roughing operation is carried out to obtain lead rough concentrate and lead roughing tailings. S3. Add zinc mineral inhibitor and collector to the lead roughing tailings obtained in step S2 in sequence. After lead scavenging operation, the scavenged tailings are lead beneficiation tailings. The lead beneficiation tailings are then processed in the zinc beneficiation operation. The scavenged tailings are returned to the previous flotation operation in sequence. S4. Add zinc mineral inhibitor to the lead rough concentrate obtained in step S2. After lead concentrate beneficiation, lead concentrate is obtained. The beneficiated middlings are returned to the previous flotation operation.

6. The application according to claim 5, characterized in that, After grinding, the finely crushed ore sample contains 60% to 80% particles with a diameter of -0.074 mm; the mass fraction of the raw ore slurry is 25% to 30%.

7. The application according to claim 6, characterized in that, The zinc mineral inhibitor is at least one of sodium sulfite and zinc sulfate.

8. The application according to claim 7, characterized in that, In step S2: the zinc mineral inhibitor is sodium sulfite and zinc sulfate; wherein the amount of sodium sulfite used is 150~250 g / t of raw ore, and the amount of zinc sulfate used is 500~1200 g / t of raw ore; the amount of collector used is 40~60 g / t of raw ore; and the flotation time for roughing operation is 2~4 min.

9. The application according to claim 8, characterized in that, In step S3: the scavenging operation is performed 1 to 2 times; wherein, in the first scavenging operation: the zinc mineral inhibitor is zinc sulfate, and the dosage is 200 to 400 g / t of raw ore, the dosage of the collector is 10 to 20 g / t of raw ore, and the flotation time is 2 to 3 min; in the second scavenging operation: the dosage of the collector is 10 to 20 g / t of raw ore, and the flotation time is 1.5 to 2.5 min.

10. The application according to claim 9, characterized in that, In step S4: the refining operation is performed 2-3 times; the first refining operation: the zinc mineral inhibitor is zinc sulfate, the dosage is 150-300 g / t of raw ore, and the flotation time is 2-4 min; the second refining operation: the zinc mineral inhibitor is zinc sulfate, the dosage is 50-150 g / t of raw ore, and the flotation time is 1.5-3 min; the third refining operation: the zinc mineral inhibitor is zinc sulfate, the dosage is 50-150 g / t of raw ore, and the flotation time is 1.5-3 min.

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