A comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores

Abstract

This invention discloses a comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores, comprising the following steps: primary grinding, rapid sulfur flotation, copper-sulfur co-flotation, copper-sulfur separation, zinc sulfide flotation, weak magnetic separation of iron, multi-stage gravity separation of cassiterite, and cassiterite flotation. This invention is adapted to the characteristics of skarn-type cassiterite polymetallic minerals, which exhibit significant differences in floatability and complex mineral types, and possesses advantages such as excellent separation performance, low processing cost, and good applicability.

Description

Technical Field

[0001] This invention belongs to the field of mining engineering technology, specifically relating to a comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores. Background Art

[0002] Zinc, copper, iron, and tin are important metallic raw materials, widely used in machinery manufacturing, military, aerospace and other fields, and are regarded as strategic mineral resources by various countries.

[0003] As my country's economy enters a new stage of high-quality development, the demand for mineral resources such as zinc, tin, copper, and iron is constantly increasing. However, with the development and utilization of mineral resources, easily beneficiated single ores are becoming increasingly rare. Therefore, it is of great significance to increase the comprehensive utilization of complex and difficult-to-beneficiate polymetallic mineral resources. Skarn-type deposits are characterized by a wide variety of valuable elements, high quality, and great comprehensive utilization value. However, due to the complexity of the ore types, the large variations in the floatability of minerals, the large differences in mineral content, and the uneven distribution of mineral grains, the flotation process is inconsistent, the separation index is poor, and the process is complex. Therefore, it is of great significance to conduct research on comprehensive recovery processes for skarn-type polymetallic ores with specific properties. Summary of the Invention

[0004] The purpose of this invention is to provide a comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores.

[0005] The objective of this invention is achieved by including rapid sulfur flotation, copper-sulfur co-flotation, and post-treatment steps, specifically including:

[0006] A. Rapid sulfur flotation:

[0007] 1) Grind the raw ore to a fineness of -0.074mm, with 60-65% of the ore being 0.074mm, to obtain material a;

[0008] 2) Add a weak collector to material a and perform flotation to obtain sulfur concentrate I and flotation tailings b;

[0009] B. Copper-sulfur co-flotation: Add inhibitors, collectors and frothers to flotation tailings b and co-flotation to obtain copper-sulfur flotation ore c and co-flotation tailings d.

[0010] C. Post-processing:

[0011] 1) The copper-sulfur flotation ore c is further refined to obtain copper-sulfur concentrate e and tailings f. The tailings f are returned to the copper-sulfur mixing step.

[0012] 2) The mixed tailings d are scavenged twice to obtain scavenged ore g1, scavenged ore g2 and tailings h. Scavenged ore g1 is returned to the copper-sulfur mixed separation step, and scavenged ore g2 is returned to the previous scavenging step.

[0013] 3) Copper-sulfur concentrate e is subjected to grinding, one roughing, two cleaning, and one scavenging to obtain copper concentrate i and sulfur concentrate II;

[0014] 4) The tailings h are subjected to one roughing, three cleaning, and two scavenging processes to obtain zinc concentrate j and tailings k;

[0015] 5) The tailings k are subjected to a first weak magnetic separation roughing and a first weak magnetic separation cleaning to obtain iron concentrate l and weak magnetic separation tailings m; the magnetic field strength of the first weak magnetic separation roughing is 1000~1500 Oe; the magnetic field strength of the first weak magnetic separation cleaning is 700~900 Oe;

[0016] 6) The weak magnetic separation tailings m are subjected to a first shaking table separation, a first-stage grinding, a second shaking table separation, a second-stage grinding, and a third shaking table separation to obtain tin concentrate I and tin tailings n;

[0017] 7) Tin tailings n are subjected to two roughing, two cleaning and one scavenging processes to obtain tin concentrate II and final tailings.

[0018] The specific steps are as follows:

[0019] A. First stage grinding: Grinding the raw ore to 60%~65% of -0.074mm;

[0020] B. Rapid sulfur flotation: The ground slurry is subjected to a first-stage flotation to obtain sulfur concentrate I;

[0021] C. Lead-sulfur mixed flotation: The sulfur rapid flotation tailings obtained in step B are subjected to one lead-sulfur mixed roughing, two lead-sulfur mixed scavenging, and one lead-sulfur mixed cleaning to obtain lead-sulfur mixed concentrate and lead-sulfur mixed flotation tailings.

[0022] D. Lead-sulfur separation flotation: The lead-sulfur mixed concentrate obtained in step C is subjected to two lead-sulfur separation processes: one roughing process and one scavenging process, to obtain copper concentrate and sulfur concentrate II.

[0023] F. Zinc sulfide flotation: The lead-sulfur mixed flotation tailings obtained in step C are subjected to one zinc sulfide roughing, two zinc sulfide scavenging, and three zinc sulfide cleaning to obtain zinc concentrate and zinc sulfide scavenging tailings.

[0024] G. Weak magnetic separation of iron: The zinc sulfide tailings obtained in step F are subjected to one weak magnetic roughing and one weak magnetic cleaning to obtain iron concentrate and weak magnetic tailings.

[0025] H. Cassiterite multi-stage gravity separation: The weak magnetic separation tailings obtained in step G are subjected to a single shaking table separation to obtain tin concentrate 1, middlings 1, and tin tailings 1; middlings 1 is subjected to three-stage grinding, and the grinding product of the three-stage grinding is subjected to a second shaking table separation to obtain tin concentrate 2, middlings 2, and tin tailings 2; middlings 2 is subjected to four-stage grinding, and the grinding product of the four-stage grinding is subjected to a third shaking table separation to obtain tin concentrate 3 and tin tailings 3; tin concentrate 1, tin concentrate 2, and tin concentrate 3 are combined to obtain tin concentrate I, and tin tailings 1, tin tailings 2, and tin tailings 3 are combined to obtain tin gravity separation tailings;

[0026] I. Cassiterite Flotation: The tin gravity separation tailings obtained in step H are subjected to two tin roughing processes, one tin scavenging process, and two tin cleaning processes to obtain tin concentrate II and the final tailings.

[0027] The weak collector pine oil mentioned in step B is used at a dosage of 25~40g / t.

[0028] Step C involves the sequential addition of a zinc sulfide inhibitor, a collector, and a foaming agent; the zinc sulfide inhibitor is one or both of zinc sulfate and XY-1, the collector is one or more of butyl xanthate, isobutyl xanthate, and isoamyl xanthate, and the foaming agent is one or more of 24K, HCCL, and MIBC.

[0029] The process conditions for the copper-sulfur mixed roughing process in step C are as follows: add 1500-2000 g / t of zinc sulfide inhibitor, stir for 3-5 min, then add 100-150 g / t of collector and 30-40 g / t of frother, and stir for 2-4 min. For the lead-sulfur mixed scavenging process, the amounts of inhibitor, collector, and frother are halved in sequence according to the copper-sulfur mixed roughing process. For the lead-sulfur mixed cleaning process, add 500-800 g / t of zinc sulfide inhibitor, stir for 3-5 min, then add 10-20 g / t of collector, and stir for 2-4 min.

[0030] In step D, the fineness of the two-stage grinding is -0.045mm (75-85%). Pyrite inhibitor and copper sulfide collector are added sequentially to the two-stage grinding product. The pyrite inhibitor is lime, and the copper sulfide collector is one or more of Z200, ethyl isobutyl xanthate, and propylene isoamyl xanthate.

[0031] The roughing process conditions for lead-sulfur separation in step D are as follows: add 2000-3000 g / t of pyrite inhibitor, stir for 3-5 min, then add 40-60 g / t of copper sulfide collector, stir for 2-4 min; the scavenging process conditions for lead-sulfur separation are as follows: add 500-600 g / t of pyrite inhibitor, stir for 3-5 min, then add 10-15 g / t of copper sulfide collector, stir for 2-4 min; the finer process conditions for lead-sulfur separation are as follows: add 800-1000 g / t of pyrite inhibitor, stir for 3-5 min, then add 5-10 g / t of copper sulfide collector, stir for 2-4 min; the finer process conditions for lead-sulfur separation are as follows: add 100-200 g / t of pyrite inhibitor, stir for 3-5 min.

[0032] In step F, zinc sulfide activator, zinc sulfide collector, and frother are added sequentially to the copper-sulfur mixed scavenging tailings. The zinc sulfide activator is copper sulfate, the zinc sulfide collector is one or both of butyl xanthate and isobutyl xanthate, and the frother is one or both of pine oil and 24K.

[0033] The process conditions for the rough selection of zinc sulfide in step F are as follows: add 300-400 g / t of zinc sulfide activator, stir for 3-5 min, then add 200-300 g / t of zinc sulfide collector and 30-40 g / t of frother, and stir for 2-4 min; the amount of zinc sulfide scavenging reagent is halved in sequence with reference to the rough selection; the process conditions for zinc sulfide fine selection 1 are as follows: add 50 g / t of zinc sulfide collector, stir for 2-4 min; zinc sulfide fine selection 2 and fine selection 3 are blank fine selections.

[0034] In step G, the magnetic field strength for roughing in weak magnetic separation is 1000~1500 Oe, and the magnetic field strength for finishing in weak magnetic separation is 800 Oe.

[0035] Step H involves three-stage grinding with a grinding fineness of -0.045mm at 70-75%, and four-stage grinding with a grinding fineness of -0.045mm at 75-80%.

[0036] In step I, an activator, a collector, and a foaming agent are added sequentially. The activator is lead nitrate, the collector is two or more of benzylarsonic acid, phenoxyoxime acid, salicylic acid, and XB-3, and the foaming agent is pine oil.

[0037] In step I, for the tin flotation roughing process 1, add 150-200 g / t of activator, stir for 3-5 min, add 200-300 g / t of collector and 20-30 g / t of frother, and stir for 2-4 min. For the tin flotation roughing process 2, add 100-150 g / t of activator, stir for 3-5 min, then add 150-200 g / t of collector and 10-20 g / t of frother, and stir for 2-4 min. For the tin flotation scavenging process, refer to the tin flotation roughing process 2 with half the amount of activator. Tin flotation cleaning process 1 and tin flotation cleaning process 2 are blank cleaning processes.

[0038] Compared with the prior art, the advantages of the present invention are:

[0039] 1. This invention utilizes the differences in mineral floatability to sequentially float away highly floatable pyrite and copper sulfide, and less floatable pyrite, zinc sulfide, magnetite, and cassiterite. This achieves effective mineral separation and offers good economic efficiency and feasibility for plant construction.

[0040] 2. The staged grinding and staged beneficiation process is well adapted to the characteristics of uneven mineral dissemination, and the process has good economic efficiency and feasibility.

[0041] 3. The process of first gravity separation and then flotation in cassiterite recovery helps to improve the cassiterite recovery index. Because the process of staged grinding and staged gravity separation separates the cassiterite with larger embedded particle size, and the tailings are separated by flotation to separate the fine cassiterite that is difficult to recover by gravity separation, this process can better achieve the recovery of cassiterite of both coarse and fine particle sizes, thereby improving the cassiterite recovery index.

[0042] 4. The two-point sulfur concentrate significantly improves the separation environment of the entire process. First, pyrite with excellent floatability is floated, while the copper-sulfur co-flotation process avoids the need to add a large amount of lime to the process, which would worsen the flotation environment and also helps to reduce reagent costs.

[0043] 5. Copper-sulfur co-concentration shortens the process length and reduces grinding and reagent costs. Attached Figure Description

[0044] Figure 1 This is a process flow diagram of the present invention. Detailed Implementation

[0045] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0046] The comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores of this invention includes rapid sulfur flotation, copper-sulfur co-flotation, and post-processing steps, specifically including:

[0047] A. Rapid sulfur flotation:

[0048] 1) Grind the raw ore to a fineness of -0.074mm, with 60-65% of the ore being 0.074mm, to obtain material a;

[0049] 2) Add a weak collector to material a and perform flotation to obtain sulfur concentrate I and flotation tailings b;

[0050] B. Copper-sulfur co-flotation: Add inhibitors, collectors and frothers to flotation tailings b and co-flotation to obtain copper-sulfur flotation ore c and co-flotation tailings d.

[0051] C. Post-processing:

[0052] 1) The copper-sulfur flotation ore c is further refined to obtain copper-sulfur concentrate e and tailings f. The tailings f are returned to the copper-sulfur mixing step.

[0053] 2) The mixed tailings d are scavenged twice to obtain scavenged ore g1, scavenged ore g2 and tailings h. Scavenged ore g1 is returned to the copper-sulfur mixed separation step, and scavenged ore g2 is returned to the previous scavenging step.

[0054] 3) Copper-sulfur concentrate e is subjected to grinding, one roughing, two cleaning, and one scavenging to obtain copper concentrate i and sulfur concentrate II;

[0055] 4) The tailings h are subjected to one roughing, three cleaning, and two scavenging processes to obtain zinc concentrate j and tailings k;

[0056] 5) The tailings k are subjected to a first weak magnetic separation roughing and a first weak magnetic separation cleaning to obtain iron concentrate l and weak magnetic separation tailings m; the magnetic field strength of the first weak magnetic separation roughing is 1000~1500 Oe; the magnetic field strength of the first weak magnetic separation cleaning is 700~900 Oe;

[0057] 6) The weak magnetic separation tailings m are subjected to a first shaking table separation, a first-stage grinding, a second shaking table separation, a second-stage grinding, and a third shaking table separation to obtain tin concentrate I and tin tailings n;

[0058] 7) Tin tailings n are subjected to two roughing, two cleaning and one scavenging processes to obtain tin concentrate II and final tailings.

[0059] The weak collector mentioned in step 2) is pine oil, and the dosage is 25~40g / t.

[0060] The inhibitor mentioned in step B is zinc sulfate and / or XY-1, with a dosage of 1500~2000 g / t; the collector is one or more of butyl xanthate, isobutyl xanthate and isopentyl xanthate, with a dosage of 100~150 g / t; the foaming agent is one or more of 24k, hccl and MIBC, with a dosage of 30~40 g / t.

[0061] The refining process described in step 1) involves adding inhibitors and collectors to copper-sulfur flotation ore c. The inhibitors are zinc sulfate and / or XY-1, with a dosage of 500-800 g / t. The collectors are one or more of butyl xanthate, isobutyl xanthate, and isopentyl xanthate, with a dosage of 10-20 g / t.

[0062] In step C, step 2), both sweeps are performed with the addition of inhibitors, collectors, and frothers. The inhibitors, collectors, and frothers are the same as those used in the copper-sulfur mixed sweep step, and their dosages are halved in the copper-sulfur mixed roughing sweep.

[0063] In step 3) of C, the grinding fineness is -0.045mm, accounting for 75-85%; the first roughing is carried out by adding pyrite inhibitor and copper sulfide collector in sequence, with the dosage being 2000-3000g / t of pyrite inhibitor and 40-60g / t of copper sulfide collector; the second cleaning is carried out by adding pyrite inhibitor and copper sulfide collector in sequence during cleaning 1, with the dosage being 800-1000g / t of pyrite inhibitor and 5-10g / t of copper sulfide collector; cleaning 2 is carried out by adding pyrite inhibitor, with the dosage being 100-200g / t of pyrite inhibitor; the first scavenging is carried out by adding pyrite inhibitor and copper sulfide collector in sequence, with the dosage being 500-600g / t of pyrite inhibitor and 10-15g / t of copper sulfide collector.

[0064] The pyrite inhibitor is lime; the copper sulfide collector is one or more of Z200, ethyl isobutyl xanthate, and propylene isopentyl xanthate.

[0065] In step 4) of C, the first roughing process involves sequentially adding zinc sulfide activator, zinc sulfide collector, and frother. The dosage of zinc sulfide activator is 300-400 g / t, the dosage of zinc sulfide collector is 200-300 g / t, and the dosage of frother is 30-40 g / t. The third refining process involves adding zinc sulfide collector during refining 1. The dosage of zinc sulfide collector is 40-60 g / t. Refining 2 and Refining 3 are blank refining processes. The second scavenging process involves sequentially adding zinc sulfide activator, zinc sulfide collector, and frother, with the dosages reduced by half compared to the roughing process. The zinc sulfide activator is copper sulfate; the zinc sulfide collector is butyl xanthate and / or isobutyl xanthate; and the frother is pine oil and / or 24K.

[0066] In step C (6), the fineness of the first-stage grinding is -0.045mm, accounting for 70-75%; the fineness of the second-stage grinding is -0.045mm, accounting for 75-80%.

[0067] In step 7) of C, the secondary roughing process involves adding an activator, collector, and frother sequentially during roughing 1, with the activator dosage being 150-200 g / t, the collector dosage being 200-300 g / t, and the frother dosage being 20-30 g / t. During roughing 2, the same activator, collector, and frother are added sequentially, with the activator dosage being 100-150 g / t, the collector dosage being 150-200 g / t, and the frother dosage being 10-20 g / t. The primary scavenging process involves adding an activator, collector, and frother sequentially, with the dosage halved compared to roughing 2. The secondary refining process involves blank refining in refining 1 and refining 2. The activator is lead nitrate; the collector is two or more of benzylarsonic acid, phenoxyxamic acid, salicylic acid, and benzoyl hydroxyxamic acid (XB-3); and the frother is pine oil.

[0068] The invention will be further illustrated below with specific implementation examples:

[0069] Example 1

[0070] A mineral sample from Wenshan, Yunnan Province, contains 0.35% copper, 26.89% iron, 4.33% zinc, and 0.98% tin. The main useful minerals are chalcopyrite, sphalerite, pyrite, magnetite, and cassiterite. The chalcopyrite grains are unevenly distributed. The above mineral sample was processed using the following steps:

[0071] A. First stage grinding: Grinding the raw ore to -0.074mm (60%);

[0072] B. Rapid sulfur flotation: The ground slurry is subjected to a first-stage flotation, 30 g / t of pine oil is added, and the mixture is stirred for 3 min to obtain sulfur concentrate I by flotation.

[0073] C. Lead-sulfur mixed flotation: The sulfur rapid flotation tailings obtained in step B are subjected to one lead-sulfur mixed roughing, two lead-sulfur mixed scavenging, and one lead-sulfur mixed cleaning to obtain lead-sulfur mixed concentrate and lead-sulfur mixed flotation tailings. The process conditions for the copper-sulfur mixed roughing in step C are: adding 2000 g / t of zinc sulfide inhibitor, stirring for 3 min, then adding 120 g / t of collector and 30 g / t of frother, and stirring for 2 min; the process conditions for the lead-sulfur mixed scavenging are: reducing the amounts of inhibitor, collector, and frother by half according to the copper-sulfur mixed roughing; the process conditions for the lead-sulfur mixed cleaning are: adding 600 g / t of zinc sulfide inhibitor, stirring for 3 min, then adding 15 g / t of collector, and stirring for 2 min.

[0074] Further, the zinc sulfide inhibitor is one or both of zinc sulfate and XY-1, the collector is one or more of butyl xanthate, isobutyl xanthate and isoamyl xanthate, and the foaming agent is one or more of 24K, HCCL and MIBC;

[0075] D. Lead-sulfur separation flotation: The lead-sulfur mixed concentrate obtained in step C is subjected to two separate flotation processes: a roughing process, a scavenging process, and a finishing process, to obtain copper concentrate and sulfur concentrate II. The roughing process for lead-sulfur separation is as follows: add 2000 g / t of pyrite inhibitor, stir for 4 min, then add 50 g / t of copper sulfide collector, and stir for 2 min. The scavenging process for lead-sulfur separation is as follows: add 600 g / t of pyrite inhibitor, stir for 5 min, then add 10 g / t of copper sulfide collector, and stir for 2 min. The finishing process for lead-sulfur separation 1 is as follows: add 900 g / t of pyrite inhibitor, stir for 3 min, then add 10 g / t of copper sulfide collector, and stir for 3 min. The finishing process for lead-sulfur separation 2 is as follows: add 200 g / t of pyrite inhibitor, and stir for 4 min.

[0076] F. Zinc sulfide flotation: The lead-sulfur mixed flotation tailings obtained in step C are subjected to one zinc sulfide roughing, two zinc sulfide scavenging, and three zinc sulfide cleaning to obtain zinc concentrate and zinc sulfide scavenging tailings 2. Zinc sulfide activator, zinc sulfide collector, and frother are added sequentially to the copper-sulfur mixed scavenging tailings 2. The zinc sulfide activator is copper sulfate, the zinc sulfide collector is one or both of butyl xanthate and isobutyl xanthate, and the frother is one or both of pine oil and 24K. Further, the zinc sulfide roughing process conditions are: adding 300 g / t of zinc sulfide activator, stirring for 4 min, then adding 200 g / t of zinc sulfide collector and 40 g / t of frother, stirring for 2 min. The dosage of zinc sulfide scavenging reagents is halved sequentially from the roughing process. The zinc sulfide cleaning 1 process conditions are: adding 50 g / t of zinc sulfide collector, stirring for 2 min. Zinc sulfide cleaning 2 and cleaning 3 are blank cleaning processes.

[0077] G. Weak magnetic separation of iron: The zinc sulfide tailings obtained in step F are subjected to one weak magnetic roughing and one weak magnetic cleaning to obtain iron concentrate and weak magnetic tailings. In step G, the magnetic field strength of the weak magnetic roughing is 1500 Oe and the magnetic field strength of the weak magnetic cleaning is 800 Oe.

[0078] H. Cassiterite Multistage Gravity Separation: The weak magnetic separation tailings obtained in step G are subjected to a single shaking table separation to obtain tin concentrate 1, middlings 1, and tin tailings 1; middlings 1 is subjected to three-stage grinding, and the grinding product from the three-stage grinding is subjected to a second shaking table separation to obtain tin concentrate 2, middlings 2, and tin tailings 2; middlings 2 is subjected to four-stage grinding, and the grinding product from the four-stage grinding is subjected to a third shaking table separation to obtain tin concentrate 3 and tin tailings 3; tin concentrate 1, tin concentrate 2, and tin concentrate 3 are combined to obtain tin concentrate I, and tin tailings 1, tin tailings 2, and tin tailings 3 are combined to obtain tin gravity separation tailings. The grinding fineness of the three-stage grinding in step H is -0.045mm 73%, and the grinding fineness of the four-stage grinding is -0.045mm 76%.

[0079] I. Cassiterite Flotation: The tin gravity separation tailings obtained in step H are subjected to two tin roughing processes, one tin scavenging process, and two tin cleaning processes to obtain tin concentrate II and final tailings. In step I, an activator, a collector, and a frother are added sequentially. The activator is lead nitrate, the collector is two or more of benzylarsonic acid, phenoxyxamic acid, salicylic acid, and XB-3, and the frother is pine oil. In step I, the tin flotation roughing process 1 adds 200 g / t of activator, stirs for 3 min, adds 300 g / t of collector and 20 g / t of frother, and stirs for 3 min. In the tin flotation roughing process 2, the activator is added 150 g / t, stirs for 3 min, then adds 200 g / t of collector and 15 g / t of frother, and stirs for 2 min. The tin flotation scavenging process conditions are the same as those for tin flotation roughing process 2, but the dosage is halved. Tin flotation cleaning process 1 and tin flotation cleaning process 2 are blank cleaning processes.

[0080] Using this process to process the ore, good indicators can be obtained: sulfur concentrate with a sulfur grade of 41.33% and a sulfur recovery rate of 75.10%; copper concentrate with a sulfur grade of 26.12% and a copper recovery rate of 82.11%; iron concentrate with a sulfur grade of 57.88% and an iron recovery rate of 85.20%; and tin concentrate with a sulfur grade of 46.98% and a tin recovery rate of 77.45%.

[0081] Example 2

[0082] A mineral sample from northern Myanmar contains 0.55% copper, 26.89% iron, 6.33% zinc, and 1.68% tin. The main useful minerals are chalcopyrite, sphalerite, pyrite, magnetite, and cassiterite. The chalcopyrite grains are unevenly distributed. The above mineral sample was processed using the following steps:

[0083] A. First stage grinding: Grinding the raw ore to -0.074mm (60%);

[0084] B. Rapid sulfur flotation: The ground slurry is subjected to a first-stage flotation, 30 g / t of pine oil is added, and the mixture is stirred for 3 min to obtain sulfur concentrate I by flotation.

[0085] C. Lead-sulfur mixed flotation: The sulfur rapid flotation tailings obtained in step B are subjected to one lead-sulfur mixed roughing, two lead-sulfur mixed scavenging, and one lead-sulfur mixed cleaning to obtain lead-sulfur mixed concentrate and lead-sulfur mixed flotation tailings. The process conditions for the copper-sulfur mixed roughing in step C are: adding 2000 g / t of zinc sulfide inhibitor, stirring for 3 min, then adding 140 g / t of collector and 30 g / t of frother, and stirring for 2 min; the dosage of inhibitor, collector, and frother in the lead-sulfur mixed scavenging process conditions are halved in sequence with respect to the copper-sulfur mixed roughing; the process conditions for the lead-sulfur mixed cleaning are: adding 800 g / t of zinc sulfide inhibitor, stirring for 3 min, then adding 15 g / t of collector, and stirring for 2 min. Further, the zinc sulfide inhibitor is one or two of zinc sulfate and XY-1, the collector is one or more of butyl xanthate, isobutyl xanthate, and isopentyl xanthate, and the frother is one or more of 24K, HCCL, and MIBC.

[0086] D. Lead-sulfur separation flotation: The lead-sulfur mixed concentrate obtained in step C is subjected to two lead-sulfur separation processes: a roughing process, a scavenging process, and a finishing process, to obtain copper concentrate and sulfur concentrate II. The roughing process for lead-sulfur separation is as follows: add 3000 g / t of pyrite inhibitor, stir for 4 min, then add 60 g / t of copper sulfide collector, and stir for 2 min. The scavenging process for lead-sulfur separation is as follows: add 600 g / t of pyrite inhibitor, stir for 5 min, then add 10 g / t of copper sulfide collector, and stir for 2 min. The finishing process for lead-sulfur separation 1 is as follows: add 1000 g / t of pyrite inhibitor, stir for 3 min, then add 10 g / t of copper sulfide collector, and stir for 3 min. The finishing process for lead-sulfur separation 2 is as follows: add 300 g / t of pyrite inhibitor, and stir for 4 min.

[0087] F. Zinc sulfide flotation: The lead-sulfur mixed flotation tailings obtained in step C are subjected to one zinc sulfide roughing, two zinc sulfide scavenging, and three zinc sulfide cleaning to obtain zinc concentrate and zinc sulfide scavenging tailings 2. Zinc sulfide activator, zinc sulfide collector, and frother are added sequentially to the copper-sulfur mixed scavenging tailings 2. The zinc sulfide activator is copper sulfate, the zinc sulfide collector is one or both of butyl xanthate and isobutyl xanthate, and the frother is one or both of pine oil and 24K. Further, the zinc sulfide roughing process conditions are: adding 300 g / t of zinc sulfide activator, stirring for 4 min, then adding 250 g / t of zinc sulfide collector and 40 g / t of frother, stirring for 2 min. The dosage of zinc sulfide scavenging reagents is halved sequentially from the roughing process. The zinc sulfide cleaning 1 process conditions are: adding 50 g / t of zinc sulfide collector, stirring for 2 min. Zinc sulfide cleaning 2 and cleaning 3 are blank cleaning processes.

[0088] G. Weak magnetic separation of iron: The zinc sulfide tailings obtained in step F are subjected to one weak magnetic roughing and one weak magnetic cleaning to obtain iron concentrate and weak magnetic tailings. In step G, the magnetic field strength of the weak magnetic roughing is 1500 Oe and the magnetic field strength of the weak magnetic cleaning is 800 Oe.

[0089] H. Cassiterite Multistage Gravity Separation: The weak magnetic separation tailings obtained in step G are subjected to a single shaking table separation to obtain tin concentrate 1, middlings 1, and tin tailings 1; middlings 1 is subjected to three-stage grinding, and the grinding product from the three-stage grinding is subjected to a second shaking table separation to obtain tin concentrate 2, middlings 2, and tin tailings 2; middlings 2 is subjected to four-stage grinding, and the grinding product from the four-stage grinding is subjected to a third shaking table separation to obtain tin concentrate 3 and tin tailings 3; tin concentrate 1, tin concentrate 2, and tin concentrate 3 are combined to obtain tin concentrate I, and tin tailings 1, tin tailings 2, and tin tailings 3 are combined to obtain tin gravity separation tailings. The grinding fineness of the three-stage grinding in step H is -0.045mm 70%, and the grinding fineness of the four-stage grinding is -0.045mm 75%.

[0090] I. Cassiterite Flotation: The tin gravity separation tailings obtained in step H are subjected to two tin roughing processes, one tin scavenging process, and two tin cleaning processes to obtain tin concentrate II and final tailings. In step I, an activator, a collector, and a frother are added sequentially. The activator is lead nitrate, the collector is two or more of benzylarsonic acid, phenoxyxamic acid, salicylic acid, and XB-3, and the frother is pine oil. In step I, the tin flotation roughing process 1 adds 220 g / t of activator and stirs for 3 min, then adds 300 g / t of collector and 30 g / t of frother and stirs for 3 min. In the tin flotation roughing process 2, the activator is added 150 g / t and stirred for 3 min, then 200 g / t of collector and 15 g / t of frother and stirs for 2 min. The tin flotation scavenging process conditions are the same as those for tin flotation roughing process 2, but the dosage is halved. Tin flotation cleaning process 1 and tin flotation cleaning process 2 are blank cleaning processes.

[0091] Using this process to process the ore, good indicators can be obtained: sulfur concentrate with a sulfur grade of 41.33% and a sulfur recovery rate of 76.23%; copper concentrate with a sulfur grade of 27.42% and a copper recovery rate of 83.45%; iron concentrate with a sulfur grade of 58.93% and an iron recovery rate of 86.11%; and tin concentrate with a sulfur grade of 50.17% and a tin recovery rate of 78.58%.

[0092] Example 3

[0093] A mineral sample from Lincang, Yunnan Province, contains 0.25% copper, 27.21% iron, 3.76% zinc, and 0.79% tin. The main useful minerals are chalcopyrite, sphalerite, pyrite, magnetite, and cassiterite. The chalcopyrite grains are unevenly distributed. The above mineral sample was processed using the following steps:

[0094] A. First stage grinding: Grinding the raw ore to -0.074mm (63%);

[0095] B. Rapid sulfur flotation: The ground slurry is subjected to a first-stage flotation, 25g / t of pine oil is added, and the mixture is stirred for 3 minutes to obtain sulfur concentrate I by flotation.

[0096] C. Lead-sulfur mixed flotation: The sulfur rapid flotation tailings obtained in step B are subjected to one lead-sulfur mixed roughing, two lead-sulfur mixed scavenging, and one lead-sulfur mixed cleaning to obtain lead-sulfur mixed concentrate and lead-sulfur mixed flotation tailings. The process conditions for the copper-sulfur mixed roughing in step C are: adding 1500 g / t of zinc sulfide inhibitor, stirring for 3 min, then adding 90 g / t of collector and 30 g / t of frother, and stirring for 2 min; the dosage of inhibitor, collector, and frother in the lead-sulfur mixed scavenging process conditions are halved in sequence with respect to the copper-sulfur mixed roughing; the process conditions for the lead-sulfur mixed cleaning are: adding 600 g / t of zinc sulfide inhibitor, stirring for 3 min, then adding 15 g / t of collector, and stirring for 2 min. Further, the zinc sulfide inhibitor is one or both of zinc sulfate and XY-1, the collector is one or more of butyl xanthate, isobutyl xanthate, and isopentyl xanthate, and the frother is one or more of 24K, HCCL, and MIBC.

[0097] D. Lead-sulfur separation flotation: The lead-sulfur mixed concentrate obtained in step C is subjected to two lead-sulfur separation processes: a roughing process, a scavenging process, and a finishing process, to obtain copper concentrate and sulfur concentrate II. The roughing process for lead-sulfur separation is as follows: add 2000 g / t of pyrite inhibitor, stir for 4 min, then add 40 g / t of copper sulfide collector, and stir for 2 min. The scavenging process for lead-sulfur separation is as follows: add 700 g / t of pyrite inhibitor, stir for 5 min, then add 10 g / t of copper sulfide collector, and stir for 2 min. The finishing process for lead-sulfur separation 1 is as follows: add 800 g / t of pyrite inhibitor, stir for 3 min, then add 10 g / t of copper sulfide collector, and stir for 3 min. The finishing process for lead-sulfur separation 2 is as follows: add 200 g / t of pyrite inhibitor, and stir for 4 min.

[0098] F. Zinc sulfide flotation: The lead-sulfur mixed flotation tailings obtained in step C are subjected to one zinc sulfide roughing, two zinc sulfide scavenging, and three zinc sulfide cleaning to obtain zinc concentrate and zinc sulfide scavenging tailings 2. Zinc sulfide activator, zinc sulfide collector, and frother are added sequentially to the copper-sulfur mixed scavenging tailings 2. The zinc sulfide activator is copper sulfate, the zinc sulfide collector is one or both of butyl xanthate and isobutyl xanthate, and the frother is one or both of pine oil and 24K. Further, the zinc sulfide roughing process conditions are: adding 280 g / t of zinc sulfide activator, stirring for 4 min, then adding 180 g / t of zinc sulfide collector and 40 g / t of frother, stirring for 2 min. The dosage of zinc sulfide scavenging reagents is halved sequentially from the roughing process. The zinc sulfide cleaning 1 process conditions are: adding 50 g / t of zinc sulfide collector, stirring for 2 min. Zinc sulfide cleaning 2 and cleaning 3 are blank cleaning processes.

[0099] G. Weak magnetic separation of iron: The zinc sulfide tailings obtained in step F are subjected to one weak magnetic roughing and one weak magnetic cleaning to obtain iron concentrate and weak magnetic tailings. In step G, the magnetic field strength of the weak magnetic roughing is 1500 Oe and the magnetic field strength of the weak magnetic cleaning is 700 Oe.

[0100] H. Cassiterite Multi-Stage Gravity Separation: The weak magnetic separation tailings obtained in step G are subjected to a single shaking table separation to obtain tin concentrate 1, middlings 1, and tin tailings 1; middlings 1 is subjected to three-stage grinding, and the grinding product from the three-stage grinding is subjected to a second shaking table separation to obtain tin concentrate 2, middlings 2, and tin tailings 2; middlings 2 is subjected to four-stage grinding, and the grinding product from the four-stage grinding is subjected to a third shaking table separation to obtain tin concentrate 3 and tin tailings 3; tin concentrate 1, tin concentrate 2, and tin concentrate 3 are combined to obtain tin concentrate I, and tin tailings 1, tin tailings 2, and tin tailings 3 are combined to obtain tin gravity separation tailings. The grinding fineness of the three-stage grinding in step H is -0.045mm 75%, and the grinding fineness of the four-stage grinding is -0.045mm 78%.

[0101] I. Cassiterite Flotation: The tin gravity separation tailings obtained in step H are subjected to two tin roughing processes, one tin scavenging process, and two tin cleaning processes to obtain tin concentrate II and final tailings. In step I, an activator, a collector, and a frother are added sequentially. The activator is lead nitrate, the collector is two or more of benzylarsonic acid, phenoxyxamic acid, salicylic acid, and XB-3, and the frother is pine oil. In step I, the tin flotation roughing process 1 adds 200 g / t of activator and stirs for 3 min, then adds 260 g / t of collector and 20 g / t of frother, and stirs for 3 min. In the tin flotation roughing process 2, the activator is added 140 g / t and stirred for 3 min, then 180 g / t of collector and 15 g / t of frother are added, and stirred for 2 min. The tin flotation scavenging process conditions are the same as those for tin flotation roughing process 2, but the dosage is halved. Tin flotation cleaning process 1 and tin flotation cleaning process 2 are blank cleaning processes.

[0102] Using this process to process the ore, good indicators can be obtained: sulfur concentrate with a sulfur grade of 39.26% and a sulfur recovery rate of 72.10%; copper concentrate with a sulfur grade of 24.12% and a copper recovery rate of 79.45%; iron concentrate with a sulfur grade of 56.88% and an iron recovery rate of 83.99%; and tin concentrate with a sulfur grade of 47.23% and a tin recovery rate of 75.69%.

Claims

1. A comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores, characterized in that, It includes rapid sulfur flotation, copper-sulfur co-flotation, and post-treatment steps, specifically including: A. Rapid sulfur flotation: 1) Grind the raw ore to a fineness of -0.074mm, with 60-65% of the ore being 0.074mm, to obtain material a; 2) Add 25~40g / t of weak collector pine oil to material a, and carry out flotation to obtain sulfur concentrate I and sulfur fast flotation tailings b; B. Copper-sulfur co-flotation roughing: Add 1500~2000 g / t of zinc sulfate and / or XY-1, 100~150 g / t of one or more of butyl xanthate, isobutyl xanthate and isoamyl xanthate, and 30~40 g / t of one or more of frothers 24K, HCCL and MIBC to the sulfur rapid flotation tailings b for co-flotation to obtain copper-sulfur co-flotation rough c and copper-sulfur co-flotation tailings d. C. Post-processing: 1) Add 500~800g / t of zinc sulfate and / or XY-1 as inhibitors and 10~20g / t of one or more of butyl xanthate, isobutyl xanthate and isoamyl xanthate as collectors to the copper-sulfur co-flotation rough c, and carry out copper-sulfur co-flotation to obtain copper-sulfur concentrate e and tailings f. Tailings f are returned to the copper-sulfur co-flotation roughing step. 2) The copper-sulfur mixed tailings d are scavenged twice to obtain scavenged ore g1, scavenged ore g2 and tailings h. Scavenged ore g1 is returned to the copper-sulfur mixed step, and scavenged ore g2 is returned to the previous scavenging step. 3) Copper-sulfur concentrate e is subjected to grinding, one roughing, two cleaning, and one scavenging to obtain copper concentrate i and sulfur concentrate II; 4) Tailings h are subjected to one roughing, three cleaning, and two scavenging processes to obtain zinc concentrate j and tailings k. The first roughing process involves sequentially adding 300-400 g / t of zinc sulfide activator, 200-300 g / t of zinc sulfide collector, and 30-40 g / t of frother. The third cleaning process involves adding 40-60 g / t of zinc sulfide collector during cleaning 1, while cleaning 2 and 3 are blank cleaning processes. The second scavenging process involves sequentially adding zinc sulfide activator, zinc sulfide collector, and frother, with the dosages halved compared to the roughing process. The zinc sulfide activator is copper sulfate; the zinc sulfide collector is butyl xanthate and / or isobutyl xanthate; and the frother is pine oil and / or 24K. 5) The tailings k are subjected to a primary magnetic separation with a magnetic field strength of 1000~1500 Oe for roughing and a primary magnetic separation with a magnetic field strength of 700~900 Oe for cleaning to obtain iron concentrate l and weak magnetic separation tailings m; 6) The weak magnetic separation tailings m are subjected to a first shaking table separation, a first-stage grinding, a second shaking table separation, a second-stage grinding, and a third shaking table separation to obtain tin concentrate I and tin tailings n; 7) Tin tailings n are subjected to two roughing, two cleaning, and one scavenging processes to obtain tin concentrate II and final tailings. The second roughing process involves adding 150-200 g / t of activator, 200-300 g / t of collector, and 20-30 g / t of frother sequentially during roughing 1. During roughing 2, 100-150 g / t of activator, 150-200 g / t of collector, and 10-20 g / t of frother sequentially are added sequentially. The second cleaning process uses cleaning 1 and cleaning 2 as blank cleaning processes. The first scavenging process involves adding activator, collector, and frother sequentially, with the dosage halved compared to roughing 2. The activator is lead nitrate; the collector is two or more of benzylarsonic acid, phenoxyxamic acid, salicylic acid, and benzoyl oxime acid; and the frother is pine oil.

2. The comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores according to claim 1, characterized in that, In step C, step 2), both sweeps are performed with the addition of inhibitors, collectors, and frothers. The inhibitors, collectors, and frothers are the same as those used in the copper-sulfur mixed sweep step, and their dosages are halved in the copper-sulfur mixed roughing sweep.

3. The comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores according to claim 1, characterized in that, In step 3) of C, the grinding fineness is -0.045mm, accounting for 75-85%; 2000-3000g / t of pyrite inhibitor lime and 40-60g / t of copper sulfide collector Z200, ethyl isobutyl xanthate, and propylene isopentyl xanthate are added sequentially for roughing; during cleaning step 1, 800-1000g / t of pyrite inhibitor lime and 5-10g / t of copper sulfide are added sequentially. The following methods are used for fine selection: collector Z200, ethyl isobutyl xanthate, and propylene isoamyl xanthate; fine selection 2 involves adding 100-200 g / t of pyrite inhibitor; and primary scavenging involves sequentially adding 500-600 g / t of pyrite inhibitor lime and 10-15 g / t of copper sulfide collector Z200, ethyl isobutyl xanthate, and propylene isoamyl xanthate.

4. The comprehensive recovery and beneficiation method for skarn-type zinc-tin-copper-iron polymetallic sulfide ores according to claim 1, characterized in that, In step C (6), the fineness of the first-stage grinding is -0.045mm, accounting for 70-75%; the fineness of the second-stage grinding is -0.045mm, accounting for 75-80%.

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