A mineral processing method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores

Abstract

This invention provides a beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores. The method employs steps including coarse grinding, copper-silver high-precision flotation, zinc-sulfur mixed flotation, classification, concentration, grinding, zinc-sulfur separation, shaking table gravity separation, middlings regrinding, flotation desulfurization, and copper-silver-sulfur separation. Addressing the characteristics of coarsely distributed cassiterite and finely distributed sulfide ores, this invention solves the problem of simultaneously recovering sulfide ores and cassiterite in tin polymetallic ores through quality-based classification, staged grinding, and centralized processing. This method ensures tin recovery while improving zinc concentrate grade by staged recovery of copper and silver with wide and fine particle sizes, achieving efficient and comprehensive recovery of valuable metals such as tin, silver, copper, and zinc, maximizing resource economic benefits, and effectively avoiding the problems of over-grinding of tin and loss of copper and silver.

Description

Technical Field

[0001] This invention belongs to the field of mineral beneficiation and processing technology, specifically relating to a beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores. Background Technology

[0002] Tin is an important metallic resource, widely used in electronics, chemicals, and other fields. my country is a country rich in tin resources, but it is also a major consumer of tin resources. With the gradual depletion of high-grade monometallic tin ore resources, associated tin ore is gradually becoming the main source of tin. Among these, the development and utilization of tin-associated polymetallic deposits has become an important direction in current mineral resource development. However, compared with monometallic tin ore, the development of such deposits faces higher technical difficulties, especially in beneficiation processes.

[0003] In existing technologies, cassiterite recovery mainly relies on gravity separation processes. For example, patent CN102658236B proposes a method to recover graded fine cassiterite minerals by gravity separation using a fine cassiterite shaking table, obtaining cassiterite rough concentrates of different particle sizes. Similarly, patent CN115814934A describes a process in which tailings slurry is uniformly stirred and fed into a hydraulic classifier. The fine sand and mud separated by the hydraulic classifier are then fed into a linear motor-driven fine sand shaking table and a grooved shaking table for separation, ultimately producing tin rough concentrate, tin middlings, and tin tailings. While gravity separation is the primary beneficiation process for cassiterite, in polymetallic sulfide ores, sulfide minerals have a high density (generally >4 g / cm³). 3 ), and the density of cassiterite (6.95 g / cm³) 3 The small differences in particle size interfered with the gravity separation of cassiterite. Furthermore, the good floatability of sulfide minerals further interfered with the separation of cassiterite during the flotation of fine-grained cassiterite. This interference not only resulted in a lower tin recovery rate but also led to the addition of more sulfide minerals to the tin concentrate, reducing its grade and value.

[0004] Furthermore, polymetallic sulfide ores often contain valuable metal resources such as copper, silver, and zinc. The value of these metal resources accounts for a high proportion of the total value of the minerals, especially in low-grade tin ores, where the metal value of sulfide ores may exceed 50%. In existing technologies, sulfide minerals are often removed without effective recovery, leading to serious resource waste.

[0005] The mineralization characteristics of these deposits result in significant differences in the grain size distribution of cassiterite and sulfide minerals. Cassiterite is coarser in distribution, while sulfide minerals (such as chalcopyrite, pyrite, and sphalerite) are finer. In actual production, grinding fineness is usually prioritized for cassiterite recovery, with some sulfide mineral recovery also considered. However, insufficient grinding liberation leads to inefficient recovery of valuable metals such as copper and silver. Some copper and silver resources end up in zinc concentrate, sulfur concentrate, and cassiterite desulfurization products, not only wasting copper and silver resources but also negatively impacting the quality of zinc concentrate.

[0006] Therefore, how to achieve efficient enrichment and recovery of valuable metals such as copper, silver, and zinc while ensuring the effective recovery of cassiterite has become a key technical issue for improving the efficiency of tin beneficiation plants. Summary of the Invention

[0007] The purpose of this invention is to address the problems of inefficient copper and silver recovery in current tin beneficiation plants, including waste of copper and silver resources, excessive impurities in zinc concentrate, and high copper and silver content in sulfur concentrate. This invention provides a beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores, achieving efficient tin recovery from these ores, reducing the silver and copper content in zinc and sulfur concentrates, increasing the copper and silver recovery rate, and simultaneously reducing impurities in zinc concentrate, ultimately achieving efficient resource utilization.

[0008] The technical solution adopted in this invention is as follows:

[0009] A mineral processing method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores includes the following steps:

[0010] S1. The raw ore is coarsely ground, then slurry-mixed and ground again to obtain the ground product;

[0011] S2. The grinding product obtained in S1 is subjected to copper-silver high flotation. The copper-silver high flotation process is to add a collector for roughing, add an inhibitor for cleaning and scavenging, and obtain silver-copper concentrate 1 and silver-copper tailings.

[0012] S3. The silver-copper tailings obtained in S2 are subjected to zinc-sulfur flotation. The zinc-sulfur flotation process is to add activator and collector for roughing, cleaning, and adding collector for scavenging to obtain zinc-sulfur flotation concentrate and zinc-sulfur flotation tailings.

[0013] S4. The zinc-sulfur mixed flotation concentrate obtained in S3 is classified to obtain coarse and fine particle products. The fine particle products are then ground to obtain the ground product.

[0014] S5. The grinding product obtained in S4 is de-treated and scrubbed before entering the zinc-sulfur separation operation. The zinc-sulfur separation process is as follows: adding inhibitors and collectors for roughing, adding inhibitors for cleaning, and adding collectors for scavenging to obtain zinc concentrate and sulfur concentrate 1.

[0015] S6. The zinc-sulfur mixed flotation tailings obtained in S3 are fed into a shaking table for gravity separation to obtain shaking table concentrate, shaking table middlings and shaking table tailings. The shaking table middlings are then ground to obtain the grinding product.

[0016] S7. The grinding product obtained in S6 is fed into the flotation desulfurization operation. The flotation desulfurization process involves adding a collector for roughing, cleaning and scavenging to obtain sulfur concentrate 2 and desulfurized tailings.

[0017] S8. After de-reagent washing, the sulfur concentrate 1 obtained in S5 and the sulfur concentrate 2 obtained in S7 are subjected to copper-silver-sulfur flotation. The copper-silver-sulfur flotation process is as follows: adding inhibitors and collectors for roughing, adding inhibitors for cleaning, and adding collectors for scavenging, to obtain silver-copper concentrate 2 and sulfur concentrate.

[0018] To address the issue of poor copper, silver, and zinc recovery, the concepts of coarse-grained feeding, staged grinding, and graded recovery were proposed. In the main tin beneficiation process, coarse-grained feeding was adopted to prevent over-grinding of cassiterite, adhering to the principle of early recovery to ensure efficient tin recovery. For tin middlings with insufficient liberation, regrinding and desulfurization were carried out, not only recovering liberated sulfide ores but also further liberating tin, thus achieving stepwise separation and enrichment of tin and sulfur. In branch processes or processes after tin beneficiation, further grinding was used to liberate copper and silver from zinc, sulfur, or gangue minerals, ultimately achieving the recovery of copper, zinc, and silver. The final process flow adopted was "coarse grinding - copper and silver high-precision flotation - zinc and sulfur mixed flotation - classification - coarse-grained return regrinding - fine-grained zinc and sulfur separation - sulfur concentrate regrinding and re-benefitting copper and silver - cassiterite shaking table gravity separation," with the use of high-efficiency reagents during flotation to achieve effective separation of copper, silver, zinc, and sulfur, while simultaneously achieving efficient tin recovery from copper-silver-zinc polymetallic ores. This not only improves the recovery rate of copper and silver, but also reduces the proportion of silver and copper in zinc concentrate and sulfur concentrate, and reduces the impurity content in zinc concentrate, thereby achieving efficient utilization of resources.

[0019] Further, the grinding concentration in step S1 is 65-85%, and the mass of particles smaller than 0.074 mm in the grinding product accounts for 45-60% of the total particle mass.

[0020] Further, in step S2, the collector is a mixture of thiocyanate and isobutyl allyl thiocarbamate in a mass ratio of 3-5:1, and the inhibitor is a mixture of sodium-containing compound A, sodium-containing compound B and zinc sulfate in a mass ratio of 1:3-5:6-10, wherein sodium-containing compound A is sodium sulfide or sodium hydrosulfide, and sodium compound B is sodium carbonate or sodium sulfite.

[0021] Thionitrile ester and isobutyl allyl thiocarbamate are highly efficient collectors for copper and silver, respectively. Moreover, the two can play a synergistic and complementary role in the recovery of silver-containing copper minerals, promoting the collection effect of copper and silver. Using only one of them will reduce the recovery rate of both copper and silver.

[0022] Further, in step S3, the activator is a copper sulfate or copper chloride solution with pH adjusted to 3-4 by sulfuric acid, the collector added in the roughing stage is sodium dimethylolpropionate or isoamyl xanthate, and the collector added in the scavenging stage is sodium dimethylolpropionate or isoamyl xanthate.

[0023] Further, the grading in step S4 is performed according to a particle size of 0.074-0.15 mm.

[0024] Furthermore, in the grinding product described in step S4, particles smaller than 0.043 mm account for 75-85% of the total particle mass.

[0025] Further, in step S5, the de-drug scrubbing is performed as follows: coconut shell activated carbon or fruit shell activated carbon is added as a de-drug agent for scrubbing, and the scrubbing time is 0.5-1 h; in the roughing stage, a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 is added as an inhibitor; in the roughing stage, a mixture of ethyl thiocyanate, α-terpene alcohol, and dithiocarbamate in a mass ratio of 2-3:1:2-3 is added as a collector; in the cleaning stage, a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 is added as an inhibitor; and in the scavenging stage, a mixture of ethyl thiocyanate, α-terpene alcohol, and dithiocarbamate in a mass ratio of 2-3:1:2-3 is added as a collector.

[0026] The combination of sodium silicate and calcium hydroxide disperses the slurry, allowing the reagent to interact more efficiently with mineral particles and reducing the amount of gangue and pyrite, which are carried or agglomerated and float to the surface. The three reagents, ethyl thiocyanate, α-terpene alcohol, and dithiocarbamate, work synergistically. Ethyl thiocyanate and dithiocarbamate form different types of covalent bonds with sphalerite, enhancing the collection effect on the minerals. Meanwhile, α-terpene alcohol produces fine foam, strengthening the connection between mineral particles and foam, thereby forming a stable bridging structure between the collector and the minerals.

[0027] Furthermore, in the grinding product described in step S6, particles smaller than 0.074 mm account for 80-90% of the total particle mass.

[0028] Further, the collector mentioned in step S7 is sodium dimethylolpropionate or isopentyl xanthate.

[0029] Further, in step S8, the de-drug scrubbing is performed as follows: coconut shell activated carbon or fruit shell activated carbon is added as a de-drug agent for scrubbing, and the scrubbing time is 1.5-2 hours; in the roughing stage, a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 is added as an inhibitor; in the roughing stage, a mixture of thiocyanate and allyl thiocarbamate in a mass ratio of 3-5:1 is added as a collector; in the cleaning stage, a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 is added as an inhibitor; and in the scavenging stage, a mixture of thiocyanate and allyl thiocarbamate in a mass ratio of 3-5:1 is added as a collector.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] (1) The copper and silver recovery rate has been significantly improved, and the benefits of the beneficiation plant have increased significantly;

[0032] (2) The copper and sulfur grades in zinc concentrate decreased significantly, while the zinc grade in zinc concentrate increased significantly.

[0033] (3) The content of valuable metals in sulfur concentrate is significantly reduced. Sulfur concentrate can be sold directly or backfilled without the need for stockpiling and further processing.

[0034] (4) The coarse particles of zinc-sulfur mixed flotation concentrate are returned to the previous stage mill, eliminating the need for separate grinding and reducing the number of mills and grinding process.

[0035] (5) Continuous centralized processing of sulfur concentrate avoids separate processing in the later stage and reduces processing costs;

[0036] (6) With the main process, grinding fineness and tin beneficiation process unchanged, only classification and regrinding and beneficiation of sulfur concentrate are added, which is beneficial to the technical transformation of similar beneficiation plants.

[0037] (7) It can improve the problem of low recovery rate of associated sulfide ore in tin mines and achieve simultaneous and efficient enrichment of tin, copper, silver and zinc. Attached Figure Description

[0038] Figure 1 This is a flowchart of the operation process of the present invention. Detailed Implementation

[0039] The present invention is further illustrated below with reference to specific embodiments. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions in the art or as recommended by the manufacturer; the raw materials and reagents used, unless otherwise specified, are all commercially available from the conventional market. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention are within the scope of protection claimed by the present invention.

[0040] Example 1

[0041] The sample was taken from the Gejiu tin-copper-zinc polymetallic mine in Yunnan Province. The main valuable minerals are cassiterite, chalcopyrite, sphalerite, argentite, and chalcopyrite. The tin grade is 0.56%, the copper grade is 0.83%, the silver grade is 103.8 g / t, and the zinc grade is 1.68%.

[0042] (1) Add water to the raw ore to adjust the slurry to a concentration of 75%, and then add 1000g / t of zinc hydroxide for grinding, so that the mass of particles smaller than 0.074mm accounts for 50% of the total particle mass, and obtain grinding product 1.

[0043] (2) Copper-silver high-flotation operation is performed on grinding product 1. 30 g / t of collector (thiocyanate: isobutyl allyl thiocarbamate mass ratio of 3:1) is added to grinding product 1. After one roughing stage, roughing concentrate and roughing tailings are obtained. 300 g / t of inhibitor (sodium sulfide: sodium carbonate: zinc sulfate mass ratio of 1:3:6) is added to the roughing concentrate. After the first cleaning stage, cleaning concentrate 1 and cleaning tailings 1 are obtained. In the roughing concentrate 1... Add 100 g / t of inhibitor (sodium sulfide:sodium carbonate:zinc sulfate mass ratio of 1:3:6), and after a second cleaning process, obtain Cleaner 2 concentrate and Cleaner 2 tailings. Add 8 g / t of collector (thiocyanate:allyl thiocarbamate isobutyl ester mass ratio of 3:1) to the rougher tailings, and after a scavenging process, obtain scavenging concentrate and scavenging tailings. The scavenging concentrate and Cleaner 1 tailings are returned to the rougher process, and the Cleaner 2 tailings are returned to the first cleaning process. The final Cleaner 2 concentrate is silver-copper concentrate 1, and the scavenging tailings are silver-copper tailings.

[0044] (3) Zinc-sulfur co-flotation is performed on the silver-copper tailings. 100 g / t of activator (copper sulfate) and 80 g / t of collector (sodium dimethylolpropionate) are added to the silver-copper tailings. After one roughing process, rough concentrate and rough tailings are obtained. The rough concentrate is then subjected to one blank cleaning process to obtain clean concentrate and clean tailings. 20 g / t of collector (sodium dimethylolpropionate) is added to the rough tailings, and after one scavenging process, scavenged concentrate and scavenged tailings are obtained. The scavenged concentrate and clean tailings are returned to the roughing process. The final clean concentrate is a zinc-sulfur co-flotation concentrate, and the scavenged tailings are zinc-sulfur co-flotation tailings.

[0045] (4) The zinc-sulfur mixed flotation concentrate is classified according to the standard of 0.074 mm to obtain coarse particles and fine particles.

[0046] (5) Put the coarse particle product into the concentration equipment for concentration to obtain concentrated underflow and overflow water. Adjust the concentration of concentrated underflow to reach the target concentration of 60%. The concentrated underflow is returned to the coarse grinding operation of S1.

[0047] (6) The fine particles are put into a grinding mill for grinding, so that the mass of particles smaller than 0.043mm accounts for 75% of the total mass of particles, and the grinding product 2 is obtained.

[0048] (7) Zinc-sulfur separation is performed on grinding product 2. After adding coconut shell activated carbon for de-processing and scrubbing for 0.5 hours, 600 g / t of inhibitor (sodium silicate: calcium hydroxide mass ratio of 1:3) and 10 g / t of collector (ethyl thiocyanate: α-terpene alcohol: dithiocarbamate mass ratio of 2:1:2) are added. After one roughing process, rough concentrate and rough tailings are obtained. 300 g / t of inhibitor (sodium silicate: calcium hydroxide mass ratio of 1:3) is added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 are obtained. 200 g / t of inhibitor (sodium silicate: calcium hydroxide mass ratio of 1:3) is added to the clean concentrate 1. Sodium silicate:calcium hydroxide (mass ratio 1:3) was used for a second cleaning process to obtain Concentrate 2 and Concentrate 2 tailings. 200 g / t of inhibitor (sodium silicate:calcium hydroxide mass ratio 1:3) was added to Concentrate 2, and a third cleaning process was performed to obtain Concentrate 3 and Concentrate 3 tailings. 2 g / t of collector (ethyl thiocyanate: α-terpene alcohol: dithiocarbamate mass ratio 2:1:2) was added to the roughing tailings, and a scavenging process was performed to obtain scavenging concentrate and scavenging tailings. The scavenging concentrate and Concentrate 1 tailings were returned to the roughing process, Concentrate 2 tailings were returned to the first cleaning process, and Concentrate 3 tailings were returned to the second cleaning process. The final Concentrate 3 obtained was zinc concentrate (zinc-silver concentrate), and the scavenging tailings were sulfur concentrate 1.

[0049] (8) The zinc-sulfur mixed flotation tailings are placed into a shaking table for shaking table gravity separation to obtain shaking table concentrate, shaking table middlings and shaking table tailings.

[0050] (9) The ore in the shaking table is put into the grinding mill for grinding, so that the mass of particles smaller than 0.074mm accounts for 90% of the total particle mass, and the grinding product 3 is obtained.

[0051] (10) Flotation desulfurization is performed on grinding product 3. 40 g / t of collector (butyl xanthate) is added to grinding product 3. After one roughing stage, roughing concentrate and roughing tailings are obtained. The roughing concentrate is then subjected to one blank cleaning stage to obtain clean concentrate and clean tailings. 10 g / t of collector (butyl xanthate) is added to the roughing tailings. After one scavenging stage, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and clean tailings are returned to the roughing operation. The final clean concentrate obtained is sulfur concentrate 2, and the scavenging tailings are desulfurized tailings. The desulfurized tailings are returned to the shaking table gravity separation operation.

[0052] (11) Copper-silver-sulfur flotation was performed on sulfur concentrate 1 and sulfur concentrate 2. After descaling and scrubbing with activated carbon from fruit shells for 1 hour, 800 g / t of inhibitor (sodium silicate:calcium hydroxide mass ratio of 1:3) and 50 g / t of collector (thiocyanate:allyl thiocarbamate isobutyl ester mass ratio of 3:1) were added. After one roughing process, rough concentrate and rough tailings were obtained. 400 g / t of inhibitor (sodium silicate:calcium hydroxide mass ratio of 1:3) was added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 were obtained. 200 g / t of inhibitor was added to the clean concentrate 1. The process involves a second cleaning process using an inhibitor (sodium silicate:calcium hydroxide mass ratio of 1:3), yielding Concentrate 2 and Concentrate 2 tailings. A 100 g / t inhibitor (sodium silicate:calcium hydroxide mass ratio of 1:3) is added to Concentrate 2, resulting in a third cleaning process to obtain Concentrate 3 and Concentrate 3 tailings. A 10 g / t collector (thiocyanate:allyl thiocarbamate isobutyl ester mass ratio of 3:1) is added to the roughing tailings, followed by a scavenging process to obtain scavenged concentrate and scavenged tailings. The scavenged concentrate and Concentrate 1 tailings are returned to the roughing operation, Concentrate 2 tailings are returned to the first cleaning operation, and Concentrate 3 tailings are returned to the second cleaning operation. The final Concentrate 3 obtained is silver-copper concentrate 2, and the scavenged tailings are sulfur concentrate.

[0053] In this embodiment, the copper-copper concentrate 1 has copper and silver grades of 12.68% and 1435.0 g / t, respectively, with copper and silver recoveries of 81.43% and 73.69%, respectively; the copper-copper concentrate 2 has copper and silver grades of 8.53% and 1123.0 g / t, respectively, with copper and silver recoveries of 8.84% and 9.30%, respectively; and the zinc-silver concentrate has zinc and silver grades of 45.68% and 356.3 g / t, respectively, with zinc and silver recoveries of 84.56% and 10.67%, respectively.

[0054] Example 2

[0055] The sample is a polymetallic tin-copper-zinc deposit in Xilingol League, Inner Mongolia. The main valuable minerals are cassiterite, chalcopyrite, sphalerite, and chalcopyrite. The tin grade is 1.32%, the copper grade is 0.78%, the silver grade is 211.8 g / t, and the zinc grade is 1.22%.

[0056] (1) Add water to the raw ore to adjust the slurry to a concentration of 65%, and then add 1500g / t of zinc hydroxide for grinding, so that the mass of particles smaller than 0.074mm accounts for 45% of the total particle mass, and obtain grinding product 1.

[0057] (2) Copper-silver high-flotation operation was performed on grinding product 1. 40 g / t of collector (thiocyanate: isobutyl allyl thiocarbamate mass ratio of 5:1) was added to grinding product 1. After one roughing stage, roughing concentrate and roughing tailings were obtained. 200 g / t of inhibitor (sodium sulfide: sodium sulfite: zinc sulfate = 1:3:6) was added to the roughing concentrate. After the first cleaning stage, cleaning concentrate 1 and cleaning tailings 1 were obtained. In the roughing concentrate 1... Adding 50 g / t of inhibitor (sodium sulfide:sodium sulfite:zinc sulfate = 1:3:6), and after a second cleaning process, we obtain Cleaner 2 concentrate and Cleaner 2 tailings. Adding 10 g / t of collector (thiocyanate:isobutyl allyl thiocarbamate mass ratio 5:1) to the rougher tailings, and after a scavenging process, we obtain scavenging concentrate and scavenging tailings. The scavenging concentrate and Cleaner 1 tailings are returned to the rougher process, while the Cleaner 2 tailings are returned to the first cleaning process. The final Cleaner 2 concentrate is silver-copper concentrate 1, and the scavenging tailings are silver-copper tailings.

[0058] (3) Zinc-sulfur co-flotation is performed on the silver-copper tailings. 80 g / t of activator (copper chloride) and 60 g / t of collector (sodium dimethylolpropionate) are added to the silver-copper tailings. After one roughing process, rough concentrate and rough tailings are obtained. The rough concentrate is then subjected to one blank cleaning process to obtain clean concentrate and clean tailings. 20 g / t of collector (sodium dimethylolpropionate) is added to the rough tailings, and after one scavenging process, scavenged concentrate and scavenged tailings are obtained. The scavenged concentrate and clean tailings are returned to the roughing process. The final clean concentrate is a zinc-sulfur co-flotation concentrate, and the scavenged tailings are zinc-sulfur co-flotation tailings.

[0059] (4) The zinc-sulfur mixed flotation concentrate is classified according to the standard of 0.15mm to obtain coarse particles and fine particles.

[0060] (5) Put the coarse particle product into the concentration equipment for concentration to obtain concentrated underflow and overflow water. Adjust the concentration of concentrated underflow to reach the target concentration of 60%. The concentrated underflow is returned to the coarse grinding operation of S1.

[0061] (6) The fine particles are put into a grinding mill for grinding, so that the mass of particles smaller than 0.043mm accounts for 85% of the total mass of particles, and the grinding product 2 is obtained.

[0062] (7) Zinc-sulfur separation is performed on grinding product 2. After adding coconut shell activated carbon for de-processing and scrubbing for 1 hour, 500 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) and 8 g / t of collector (ethyl thiocyanate: α-terpene alcohol: dithiocarbamate = 3:1:3) are added. After one roughing process, rough concentrate and rough tailings are obtained. 200 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) is added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 are obtained. 100 g / t of inhibitor (sodium silicate) is added to the clean concentrate 1. The mixture was prepared by a second cleaning process using a sodium silicate:calcium hydroxide ratio of 1:5. This yielded Concentrate 2 and Concentrate 2 tailings. A 100 g / t inhibitor (sodium silicate:calcium hydroxide = 1:5) was added to Concentrate 2. This resulted in a third cleaning process, yielding Concentrate 3 and Concentrate 3 tailings. A 2 g / t collector (ethyl thiocyanate: α-terpene alcohol: dithiocarbamate = 3:1:3) was added to the roughing tailings. This resulted in a scavenging concentrate and scavenging tailings. The scavenging concentrate and Concentrate 1 tailings were returned to the roughing operation, Concentrate 2 tailings were returned to the first cleaning operation, and Concentrate 3 tailings were returned to the second cleaning operation. The final Concentrate 3 was a zinc concentrate (zinc-silver concentrate), and the scavenging tailings were sulfur concentrate 1.

[0063] (8) The zinc-sulfur mixed flotation tailings are placed into a shaking table for shaking table gravity separation to obtain shaking table concentrate, shaking table middlings and shaking table tailings.

[0064] (9) The ore in the shaking table is put into the grinding mill for grinding, so that the mass of particles smaller than 0.074mm accounts for 80% of the total particle mass, and the grinding product 3 is obtained.

[0065] (10) Flotation desulfurization is performed on grinding product 3. 30 g / t of collector (butyl xanthate) is added to grinding product 3. After one roughing stage, roughing concentrate and roughing tailings are obtained. The roughing concentrate is then subjected to one blank cleaning stage to obtain clean concentrate and clean tailings. 10 g / t of collector (butyl xanthate) is added to the roughing tailings, and after one scavenging stage, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and clean tailings are returned to the roughing operation. The final clean concentrate obtained is sulfur concentrate 2, and the scavenging tailings are desulfurized tailings. The desulfurized tailings are returned to the shaking table gravity separation operation.

[0066] (11) Copper-silver-sulfur flotation was performed on sulfur concentrate 1 and sulfur concentrate 2. After dewatering and scrubbing with activated carbon from fruit shells for 1.5 hours, 600 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) and 40 g / t of collector (thiocyanate: isobutyl allyl thiocarbamate = 5:1) were added. After one roughing process, rough concentrate and rough tailings were obtained. 300 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) was added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 were obtained. 150 g / t of... An inhibitor (sodium silicate: calcium hydroxide = 1:5) was added. After a second cleaning process, concentrate 2 and tailings 2 were obtained. 100 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) was added to concentrate 2, and after a third cleaning process, concentrate 3 and tailings 3 were obtained. 8 g / t of collector (thiocyanate: isobutyl allyl thiocarbamate = 5:1) was added to the roughing tailings. After a scavenging process, scavenging concentrate and tailings were obtained. The scavenging concentrate and tailings 1 were returned to the roughing process, the tailings 2 were returned to the first cleaning process, and the tailings 3 were returned to the second cleaning process. The final concentrate 3 was silver-copper concentrate 2, and the scavenging tailings were sulfur concentrate.

[0067] In this embodiment, the copper-copper concentrate 1 has copper and silver grades of 12.55% and 3268.5 g / t, respectively, with copper and silver recoveries of 76.95% and 76.68%, respectively; the copper-copper concentrate 2 has copper and silver grades of 8.36% and 2341.8 g / t, respectively, with copper and silver recoveries of 9.22% and 9.50%, respectively; and the zinc-silver concentrate has zinc and silver grades of 46.32% and 865.9 g / t, respectively, with zinc and silver recoveries of 78.97% and 8.50%, respectively.

[0068] Example 3

[0069] The sample is a polymetallic tin-copper-zinc deposit in Xilingol League, Inner Mongolia. The main valuable minerals are cassiterite, chalcopyrite, lapis lazuli, sphalerite, etc. The tin grade is 1.03%, the copper grade is 0.67%, the silver grade is 158.9 g / t, and the zinc grade is 0.95%.

[0070] (1) Add water to the raw ore to adjust the slurry to a concentration of 85%, and then add 1300g / t of zinc hydroxide for grinding, so that the mass of particles smaller than 0.074mm accounts for 60% of the total particle mass, and obtain grinding product 1.

[0071] (2) Copper-silver high-flotation operation was performed on grinding product 1. 40 g / t of collector (thiocyanate: isobutyl allyl thiocarbamate = 3:1) was added to grinding product 1. After one roughing stage, roughing concentrate and roughing tailings were obtained. 300 g / t of inhibitor (sodium hydrosulfide: sodium carbonate: zinc sulfate = 1:5:10) was added to the roughing concentrate. After the first cleaning stage, cleaning concentrate 1 and cleaning tailings 1 were obtained. Further cleaning was performed on the roughing concentrate 1. A 100 g / t inhibitor (sodium hydrosulfide:sodium carbonate:zinc sulfate = 1:5:10) is added. After a second cleaning process, concentrate 2 and tailings 2 are obtained. A 10 g / t collector (thiocyanate:isobutyl allyl thiocarbamate = 3:1) is added to the roughing tailings. After a scavenging process, scavenging concentrate and tailings are obtained. The scavenging concentrate and tailings 1 are returned to the roughing operation, while the tailings 2 are returned to the first cleaning operation. The final concentrate 2 is silver-copper concentrate 1, and the scavenging tailings are silver-copper tailings.

[0072] (3) Zinc-sulfur co-flotation is performed on the silver-copper tailings. 100 g / t of activator (copper sulfate) and 70 g / t of collector (isoamyl xanthate) are added to the silver-copper tailings. After one roughing process, rough concentrate and rough tailings are obtained. The rough concentrate is then subjected to one blank cleaning process to obtain clean concentrate and clean tailings. 15 g / t of collector (isoamyl xanthate) is added to the rough tailings, and after one scavenging process, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and clean tailings are returned to the roughing process. The final clean concentrate is a zinc-sulfur co-flotation concentrate, and the scavenging tailings are zinc-sulfur co-flotation tailings.

[0073] (4) The zinc-sulfur mixed flotation concentrate is classified according to the standard of 0.10mm to obtain coarse particles and fine particles.

[0074] (5) Put the coarse particle product into the concentration equipment for concentration to obtain concentrated underflow and overflow water. Adjust the concentration of concentrated underflow to reach the target concentration of 70%. The concentrated underflow is returned to the coarse grinding operation of S1.

[0075] (6) The fine particles are put into a grinding mill for grinding, so that the mass of particles smaller than 0.043mm accounts for 80% of the total mass of particles, and the grinding product 2 is obtained.

[0076] (7) Zinc-sulfur separation is performed on grinding product 2. After adding coconut shell activated carbon for de-processing and scrubbing for 1 hour, 600 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) and 12 g / t of collector (ethyl thiocyanate: α-terpene alcohol: dithiocarbamate = 3:1:3) are added. After one roughing process, rough concentrate and rough tailings are obtained. 200 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) is added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 are obtained. 100 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) is added to the clean concentrate 1. Sodium:calcium hydroxide (1:3) was used for a second cleaning process to obtain Concentrate 2 and Concentrate 2 tailings. 100 g / t of inhibitor (sodium silicate:calcium hydroxide = 1:3) was added to Concentrate 2, and a third cleaning process was performed to obtain Concentrate 3 and Concentrate 3 tailings. 2 g / t of collector (ethyl thiocyanate: α-terpene alcohol: dithiocarbamate = 3:1:3) was added to the roughing tailings, and a scavenging process was performed to obtain scavenging concentrate and scavenging tailings. The scavenging concentrate and Concentrate 1 tailings were returned to the roughing process, the Concentrate 2 tailings were returned to the first cleaning process, and the Concentrate 3 tailings were returned to the second cleaning process. The final Concentrate 3 was obtained as zinc concentrate (zinc-silver concentrate), and the scavenging tailings were obtained as sulfur concentrate 1.

[0077] (8) The zinc-sulfur mixed flotation tailings are placed into a shaking table for shaking table gravity separation to obtain shaking table concentrate, shaking table middlings and shaking table tailings.

[0078] (9) The ore in the shaking table is put into the grinding mill for grinding, so that the mass of particles smaller than 0.074mm accounts for 90% of the total particle mass, and the grinding product 3 is obtained.

[0079] (10) Flotation desulfurization is performed on grinding product 3. 40 g / t of collector (butyl xanthate) is added to grinding product 3. After one roughing stage, roughing concentrate and roughing tailings are obtained. The roughing concentrate is then subjected to one blank cleaning stage to obtain clean concentrate and clean tailings. 10 g / t of collector (butyl xanthate) is added to the roughing tailings. After one scavenging stage, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and clean tailings are returned to the roughing operation. The final clean concentrate obtained is sulfur concentrate 2, and the scavenging tailings are desulfurized tailings. The desulfurized tailings are returned to the shaking table gravity separation operation.

[0080] (11) Copper-silver-sulfur flotation was carried out on sulfur concentrate 1 and sulfur concentrate 2. After dewatering and scrubbing with activated carbon from fruit shells for 2 hours, 800 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) and 30 g / t of collector (thiocyanate: isobutyl allyl thiocarbamate = 3:1) were added. After one roughing process, rough concentrate and rough tailings were obtained. 500 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) was added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 were obtained. 300 g / t of inhibitor was added to the clean concentrate 1. The formulation (sodium silicate: calcium hydroxide = 1:3) was used for a second cleaning process to obtain Concentrate 2 and Concentrate 2 tailings. 200 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) was added to Concentrate 2, and a third cleaning process was performed to obtain Concentrate 3 and Concentrate 3 tailings. 8 g / t of collector (thiocyanate: isobutyl allyl thiocarbamate = 3:1) was added to the roughing tailings, and a scavenging process was performed to obtain scavenging concentrate and scavenging tailings. The scavenging concentrate and Concentrate 1 tailings were returned to the roughing process, the Concentrate 2 tailings were returned to the first cleaning process, and the Concentrate 3 tailings were returned to the second cleaning process. The final Concentrate 3 obtained was silver-copper concentrate 2, and the scavenging tailings were sulfur concentrate.

[0081] In this embodiment, the copper-copper concentrate 1 has copper and silver grades of 12.855% and 2869.5 g / t, respectively, with copper and silver recoveries of 75.76% and 71.33%, respectively; the copper-copper concentrate 2 has copper and silver grades of 9.35% and 2256.3 g / t, respectively, with copper and silver recoveries of 10.47% and 10.65%, respectively; and the zinc-silver concentrate has zinc and silver grades of 43.68% and 783.6 g / t, respectively, with zinc and silver recoveries of 80.46% and 8.63%, respectively.

[0082] Comparative Example 1

[0083] The same sample as in Example 1 was selected, namely the Gejiu tin-copper-zinc polymetallic mine in Yunnan, with a tin grade of 0.56%, a copper grade of 0.83%, a silver grade of 103.8 g / t, and a zinc grade of 1.68%.

[0084] The copper, silver, and zinc are recovered using conventional processes and reagent regimens. The specific steps are as follows:

[0085] (1) Add water to the raw ore to adjust the slurry to a concentration of 75%, and grind it until the mass of particles smaller than 0.074 mm accounts for 50% of the total particle mass, to obtain grinding product 1.

[0086] (2) Copper-silver high-flotation operation is performed on grinding product 1. 800 g / t of inhibitor (sodium carbonate: zinc sulfate mass ratio of 1:2) and 30 g / t of collector (thiocyanate) are added to the grinding product. After one roughing operation, rough concentrate and rough tailings are obtained. 300 g / t of inhibitor (sodium carbonate: zinc sulfate mass ratio of 1:2) is added to the rough concentrate. After one cleaning operation, fine concentrate 1 and fine concentrate 1 are obtained. 100 g / t of inhibitor (sodium carbonate: zinc sulfate mass ratio of 1:2) is added to the rough concentrate. After a second cleaning operation, fine concentrate 2 and fine concentrate 2 are obtained. 8 g / t of collector (thiocyanate) is added to the rough tailings. After one scavenging operation, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and fine concentrate 1 tailings are returned to the roughing operation, and fine concentrate 2 tailings are returned to the first cleaning operation. The final selected concentrate 2 was silver-copper concentrate, and the scavenged tailings were silver-copper tailings.

[0087] (3) Zinc-sulfur co-flotation is performed on the silver-copper tailings. 100 g / t of activator (copper sulfate) and 80 g / t of collector (butyl xanthate) are added to the silver-copper tailings. After one roughing process, rough concentrate and rough tailings are obtained. The rough concentrate is then subjected to one blank cleaning process to obtain clean concentrate and clean tailings. 20 g / t of collector (butyl xanthate) is added to the rough tailings, and after one scavenging process, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and clean tailings are returned to the roughing process. The final clean concentrate is a zinc-sulfur co-flotation concentrate, and the scavenging tailings are zinc-sulfur co-flotation tailings.

[0088] (4) Direct zinc-sulfur separation is performed on the zinc-sulfur mixed flotation concentrate. The mixed flotation concentrate is ground until the mass of particles smaller than 0.043 mm accounts for 75% of the total particle mass, to obtain grinding product 2. Coconut shell activated carbon is added to grinding product 2 for de-treatment and scrubbing for 1 hour, followed by the addition of 1000 g / t of inhibitor (lime) and 12 g / t of collector (ethyl thiocyanate). After one roughing process, roughing concentrate and roughing tailings are obtained. 200 g / t of inhibitor (lime) is added to the roughing concentrate, and after the first cleaning process, cleaning concentrate 1 and cleaning tailings 1 are obtained. In the process of refining concentrate 1, 100 g / t of depressant (lime) is added. After a second refining process, concentrate 2 and tailings 2 are obtained. In the same process, 100 g / t of depressant (lime) is added to concentrate 2. After a third refining process, concentrate 3 and tailings 3 are obtained. In the roughing tailings, 2 g / t of collector (ethyl thiocyanate) is added. After a scavenging process, scavenged concentrate and tailings 3 are obtained. The scavenged concentrate and tailings 1 are returned to the roughing process, the tailings 2 are returned to the first refining process, and the tailings 3 are returned to the second refining process. The final concentrate 3 is a zinc-silver concentrate, and the scavenged tailings are a sulfur concentrate.

[0089] In the silver-copper concentrate obtained in this comparative example, the copper grade is 10.68% and the silver grade is 1134.8 g / t, with a copper recovery rate of 72.05% and a silver recovery rate of 61.22%. In the zinc-silver concentrate, the zinc grade is 38.65% and the silver grade is 318.5 g / t, with a zinc recovery rate of 71.55% and a silver recovery rate of 9.54%.

[0090] Comparative Example 2

[0091] The same sample as in Example 1 was selected, namely the Gejiu tin-copper-zinc polymetallic mine in Yunnan, with a tin grade of 0.56%, a copper grade of 0.83%, a silver grade of 103.8 g / t, and a zinc grade of 1.68%.

[0092] The copper, silver, and zinc were recovered using conventional processes and a new reagent system as described in Example 1. The specific steps are as follows:

[0093] (1) Add water to the raw ore to adjust the slurry to a concentration of 75%, so that the mass of particles smaller than 0.074 mm accounts for 50% of the total particle mass, and obtain grinding product 1.

[0094] (2) Copper-silver high-flotation is performed on grinding product 1. 30 g / t of collector (thiocyanate: isobutyl allyl thiocarbamate mass ratio of 3:1) is added to the grinding product. After one roughing stage, roughing concentrate and roughing tailings are obtained. 300 g / t of depressant (sodium sulfide: sodium carbonate: zinc sulfate mass ratio of 1:3:6) is added to the roughing concentrate. After the first cleaning stage, cleaning concentrate 1 and cleaning tailings 1 are obtained. Further depressant is added to the roughing concentrate 1. A 100 g / t inhibitor (sodium sulfide:sodium carbonate:zinc sulfate mass ratio of 1:3:6) is added. After a second cleaning process, concentrate 2 and tailings 2 are obtained. An 8 g / t collector (thiocyanate:allyl thiocarbamate isobutyl ester mass ratio of 3:1) is added to the roughing tailings. After a scavenging process, scavenging concentrate and tailings are obtained. The scavenging concentrate and concentrate 1 tailings are returned to the roughing operation, while concentrate 2 tailings are returned to the first cleaning operation. The final concentrate 2 is a silver-copper concentrate, and the scavenging tailings are silver-copper tailings.

[0095] (3) Zinc-sulfur co-flotation is performed on the silver-copper tailings. 100 g / t of activator (copper sulfate) and 80 g / t of collector (sodium dimethylolpropionate) are added to the silver-copper tailings. After one roughing process, rough concentrate and rough tailings are obtained. The rough concentrate is then subjected to one blank cleaning process to obtain clean concentrate and clean tailings. 20 g / t of collector (sodium dimethylolpropionate) is added to the rough tailings, and after one scavenging process, scavenged concentrate and scavenged tailings are obtained. The scavenged concentrate and clean tailings are returned to the roughing process. The final clean concentrate is a zinc-sulfur co-flotation concentrate, and the scavenged tailings are zinc-sulfur co-flotation tailings.

[0096] (4) Zinc-sulfur separation is performed on the zinc-sulfur mixed flotation concentrate. The mixed flotation concentrate is ground until the mass of particles smaller than 0.043 mm accounts for 75% of the total particle mass, to obtain grinding product 2. Coconut shell activated carbon is added to grinding product 2 for de-processing and scrubbing for 0.5 h, followed by the addition of 600 g / t of inhibitor (sodium silicate:calcium hydroxide mass ratio of 1:3) and 10 g / t of collector (ethyl thiocyanate: α-terpene alcohol: dithiocarbamate mass ratio of 2:1:2). After one roughing process, rough concentrate and rough tailings are obtained. 300 g / t of inhibitor (sodium silicate:calcium hydroxide mass ratio of 1:3) is added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 are obtained. 200 g / t of inhibitor (sodium silicate:calcium hydroxide mass ratio of 1:3) was added to the concentrate of the first refinement. After a second refinement, concentrate of the second refinement and tailings of the second refinement were obtained. 200 g / t of inhibitor (sodium silicate:calcium hydroxide mass ratio of 1:3) was added to the concentrate of the second refinement. After a third refinement, concentrate of the third refinement and tailings of the third refinement were obtained. 2 g / t of collector (ethyl thiocyanate: α-terpene alcohol: dithiocarbamate mass ratio of 2:1:2) was added to the rougher tailings. After a scavenging process, scavenged concentrate and scavenged tailings were obtained. The scavenged concentrate and tailings of the first refinement were returned to the rougher process, the tailings of the second refinement were returned to the first refinement process, and the tailings of the third refinement were returned to the second refinement process. The final concentrate of the third refinement was zinc concentrate (zinc-silver concentrate), and the scavenged tailings were sulfur concentrate.

[0097] The silver-copper concentrate obtained in this comparative example has a copper grade of 12.55% and a silver grade of 1428.50 g / t, with a copper recovery rate of 80.59% and a silver recovery rate of 73.35%. The zinc-silver concentrate has a zinc grade of 42.55% and a silver grade of 310.5 g / t, with a zinc recovery rate of 75.98% and a silver recovery rate of 8.97%.

[0098] Comparative Example 3

[0099] The same sample as in Example 1 was selected, namely the Gejiu tin-copper-zinc polymetallic mine in Yunnan, with a tin grade of 0.56%, a copper grade of 0.83%, a silver grade of 103.8 g / t, and a zinc grade of 1.68%.

[0100] The novel process method described in Example 1, along with conventional reagent formulations, was used to recover copper, silver, and zinc. The specific steps are as follows:

[0101] (1) Add water to the raw ore to adjust the slurry to a concentration of 75%, and then add 1000g / t of zinc hydroxide for grinding, so that the mass of particles smaller than 0.074mm accounts for 50% of the total particle mass, and obtain grinding product 1.

[0102] (2) Copper-silver high-flotation is performed on grinding product 1. 30 g / t of collector (thiocyanate) is added to grinding product 1. After one roughing process, rough concentrate and rough tailings are obtained. 300 g / t of depressant (sodium carbonate:zinc sulfate mass ratio of 1:2) is added to the rough concentrate. After one cleaning process, concentrate 1 and concentrate 1 tailings are obtained. 100 g / t of depressant (sodium carbonate:zinc sulfate mass ratio of 1:2) is added to the rough concentrate. After a second cleaning process, concentrate 2 and concentrate 2 tailings are obtained. 8 g / t of collector (thiocyanate) is added to the rough tailings. After one scavenging process, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and concentrate 1 tailings are returned to the roughing process, and concentrate 2 tailings are returned to the first cleaning process. The final concentrate 2 is silver-copper concentrate 1, and the scavenging tailings are silver-copper tailings.

[0103] (3) Zinc-sulfur co-flotation is performed on the silver-copper tailings. 100 g / t of activator (copper sulfate) and 80 g / t of collector (butyl xanthate) are added to the silver-copper tailings. After one roughing process, rough concentrate and rough tailings are obtained. The rough concentrate is then subjected to one blank cleaning process to obtain clean concentrate and clean tailings. 20 g / t of collector (butyl xanthate) is added to the rough tailings, and after one scavenging process, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and clean tailings are returned to the roughing process. The final clean concentrate is a zinc-sulfur co-flotation concentrate, and the scavenging tailings are zinc-sulfur co-flotation tailings.

[0104] (4) The zinc-sulfur mixed flotation concentrate is classified according to the standard of 0.074 mm to obtain coarse particles and fine particles.

[0105] (5) Put the coarse particle product into the concentration equipment for concentration to obtain concentrated underflow and overflow water. Adjust the concentration of concentrated underflow to reach the target concentration of 60%. The concentrated underflow is returned to the coarse grinding operation in step 1.

[0106] (6) The fine particles are put into a grinding mill for grinding, so that the mass of particles smaller than 0.043mm accounts for 75% of the total mass of particles, and the grinding product 2 is obtained.

[0107] (7) Zinc-sulfur separation is performed on grinding product 2. After adding coconut shell activated carbon for de-treatment and scrubbing for 0.5 h, 600 g / t of inhibitor (lime) and 10 g / t of collector (butyl xanthate) are added. After one roughing process, rough concentrate and rough tailings are obtained. 300 g / t of inhibitor (lime) is added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 are obtained. 200 g / t of inhibitor (lime) is added to the clean concentrate 1. The roughing process involves a second cleaning process to obtain Concentrate 2 and Concentrate 2 tailings. 200 g / t of depressant (lime) is added to Concentrate 2, and a third cleaning process is performed to obtain Concentrate 3 and Concentrate 3 tailings. 2 g / t of collector (butyl xanthate) is added to the roughing tailings, and a scavenging process is performed to obtain scavenging concentrate and scavenging tailings. The scavenging concentrate and Concentrate 1 tailings are returned to the roughing process, Concentrate 2 tailings are returned to the first cleaning process, and Concentrate 3 tailings are returned to the second cleaning process. The final Concentrate 3 is a zinc concentrate (zinc-silver concentrate), and the scavenging tailings are sulfur concentrate 1.

[0108] (8) The zinc-sulfur mixed flotation tailings are placed into a shaking table for shaking table gravity separation to obtain shaking table concentrate, shaking table middlings and shaking table tailings.

[0109] (9) The ore in the shaking table is put into the grinding mill for grinding, so that the mass of particles smaller than 0.074mm accounts for 90% of the total particle mass, and the grinding product 3 is obtained.

[0110] (10) Flotation desulfurization is performed on grinding product 3. 40 g / t of collector (butyl xanthate) is added to grinding product 3. After one roughing stage, roughing concentrate and roughing tailings are obtained. The roughing concentrate is then subjected to one blank cleaning stage to obtain clean concentrate and clean tailings. 10 g / t of collector (butyl xanthate) is added to the roughing tailings. After one scavenging stage, scavenging concentrate and scavenging tailings are obtained. The scavenging concentrate and clean tailings are returned to the roughing operation. The final clean concentrate obtained is sulfur concentrate 2, and the scavenging tailings are desulfurized tailings. The desulfurized tailings are returned to the shaking table gravity separation operation.

[0111] (11) Copper-silver-sulfur flotation was carried out on sulfur concentrate 1 and sulfur concentrate 2. After adding coconut shell activated carbon for de-removal and scrubbing for 1 hour, 800 g / t of inhibitor (lime) and 50 g / t of collector (thiocyanate) were added. After one roughing process, rough concentrate and rough tailings were obtained. 400 g / t of inhibitor (lime) was added to the rough concentrate. After the first cleaning process, clean concentrate 1 and clean tailings 1 were obtained. 200 g / t of inhibitor was added to the clean concentrate 1. The process involves a second cleaning process using an agent (lime) to obtain Concentrate 2 and Concentrate 2 tailings. A 100 g / t depressant (lime) is added to Concentrate 2, and the process is repeated a third time to obtain Concentrate 3 and Concentrate 3 tailings. A 10 g / t collector (thiocyanate) is added to the roughing tailings, and the process is repeated a third time to obtain scavenging concentrate and scavenging tailings. The scavenging concentrate and Concentrate 1 tailings are returned to the roughing operation, the Concentrate 2 tailings are returned to the first cleaning operation, and the Concentrate 3 tailings are returned to the second cleaning operation. The final Concentrate 3 is silver-copper concentrate 2, and the scavenging tailings are sulfur concentrate.

[0112] In the silver-copper concentrate 1 obtained in this comparative example, the copper and silver grades were 10.85% and 1121.3 g / t, respectively, and the copper and silver recoveries were 78.43% and 64.82%, respectively; in the silver-copper concentrate 2, the copper and silver grades were 6.73% and 956.3 g / t, respectively, and the copper and silver recoveries were 4.86% and 5.52%, respectively; in the zinc-silver concentrate, the zinc and silver grades were 43.12% and 356.3 g / t, respectively, and the zinc and silver recoveries were 78.28% and 10.77%, respectively.

[0113] By observing the indicators of silver-copper concentrate and zinc-silver concentrate separated from the same type of resources in different producing areas in Examples 1, 2 and 3 of the present invention, it can be seen that the method of the present invention obtains high-grade silver-copper concentrate and zinc-silver concentrate with high recovery rate.

[0114] Comparative Examples 1-3 and Example 1 used the same samples for mineral processing and reagent testing. Comparative Example 1 simplified the process, directly proceeding to zinc-sulfur separation after zinc-sulfur separation and zinc-sulfur co-flotation, omitting copper-silver-sulfur flotation. The collector and depressant were replaced with conventional reagents. Ultimately, the grades and recoveries of silver and copper in the silver-copper concentrate obtained in Comparative Example 1 decreased, while the grades and recoveries of zinc and silver in the zinc-silver concentrate also decreased to varying degrees. Comparative Example 2 only simplified the process, directly proceeding to zinc-sulfur separation after zinc-sulfur separation and zinc-sulfur co-flotation, omitting copper-silver-sulfur flotation. The grades and recoveries of zinc and silver in the final zinc-silver concentrate decreased. Comparative Example 3 used the same process as Example 1, except that the collector and depressant were replaced with conventional reagents. The grades and recoveries of silver and copper in the final silver-copper concentrate decreased to varying degrees, and the grades and recoveries of zinc and silver in the final zinc-silver concentrate also decreased.

Claims

1. A mineral processing method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores, characterized in that, Includes the following steps: S1. The raw ore is coarsely ground, then slurry-mixed and ground again to obtain the ground product; S2. The grinding product obtained in S1 is subjected to copper-silver high flotation. The copper-silver high flotation process is to add a collector for roughing, add an inhibitor for cleaning and scavenging, and obtain silver-copper concentrate 1 and silver-copper tailings. S3. The silver-copper tailings obtained in S2 are subjected to zinc-sulfur flotation. The zinc-sulfur flotation process is to add activator and collector for roughing, cleaning, and adding collector for scavenging to obtain zinc-sulfur flotation concentrate and zinc-sulfur flotation tailings. S4. The zinc-sulfur mixed flotation concentrate obtained in S3 is classified to obtain coarse and fine particle products. The fine particle products are then ground to obtain the ground product. S5. The grinding product obtained in S4 is de-treated and scrubbed before entering the zinc-sulfur separation operation. The zinc-sulfur separation process is as follows: adding inhibitors and collectors for roughing, adding inhibitors for cleaning, and adding collectors for scavenging to obtain zinc concentrate and sulfur concentrate 1. S6. The zinc-sulfur mixed flotation tailings obtained in S3 are fed into a shaking table for gravity separation to obtain shaking table concentrate, shaking table middlings and shaking table tailings. The shaking table middlings are then ground to obtain the grinding product. S7. The grinding product obtained in S6 is fed into the flotation desulfurization operation. The flotation desulfurization process involves adding a collector for roughing, cleaning and scavenging to obtain sulfur concentrate 2 and desulfurized tailings. S8. After de-reagent washing, the sulfur concentrate 1 obtained in S5 and the sulfur concentrate 2 obtained in S7 are subjected to copper-silver-sulfur flotation. The copper-silver-sulfur flotation process is as follows: adding inhibitors and collectors for roughing, adding inhibitors for cleaning, and adding collectors for scavenging, to obtain silver-copper concentrate 2 and sulfur concentrate.

2. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, The grinding concentration in step S1 is 65-85%, and the mass of particles smaller than 0.074 mm in the grinding product accounts for 45-60% of the total particle mass.

3. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, In step S2, the collector is a mixture of thiocyanate and isobutyl allyl thiocarbamate in a mass ratio of 3-5:1, and the inhibitor is a mixture of sodium-containing compound A, sodium-containing compound B and zinc sulfate in a mass ratio of 1:3-5:6-10, wherein sodium-containing compound A is sodium sulfide or sodium hydrosulfide, and sodium compound B is sodium carbonate or sodium sulfite.

4. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, In step S3, the activator is a copper sulfate or copper chloride solution with pH adjusted to 3-4 by sulfuric acid, the collector added in the roughing stage is sodium dimethylolpropionate or isoamyl xanthate, and the collector added in the scavenging stage is sodium dimethylolpropionate or isoamyl xanthate.

5. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, The grading in step S4 is performed according to a particle size of 0.074-0.15 mm.

6. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, In step S4, particles smaller than 0.043 mm account for 75-85% of the total particle mass of the grinding product.

7. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, In step S5, the de-drug scrubbing is performed by adding coconut shell activated carbon or fruit shell activated carbon as a de-drug agent for scrubbing for 0.5-1 hours. In the roughing stage, a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 is added as an inhibitor. In the roughing stage, a mixture of ethyl thiocyanate, α-terpene alcohol and dithiocarbamate in a mass ratio of 2-3:1:2-3 is added as a collector. In the cleaning stage, a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 is added as an inhibitor. In the scavenging stage, a mixture of ethyl thiocyanate, α-terpene alcohol and dithiocarbamate in a mass ratio of 2-3:1:2-3 is added as a collector.

8. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, In step S6, particles smaller than 0.074 mm account for 80-90% of the total particle mass of the grinding product.

9. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, The collector mentioned in step S7 is sodium dimethylolpropionate or isopentyl xanthate.

10. The beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores according to claim 1, characterized in that, In step S8, the de-drug scrubbing is performed as follows: coconut shell activated carbon or fruit shell activated carbon is added as a de-drug agent for scrubbing, and the scrubbing time is 1.5-2 hours; in the roughing stage, a mixture of sodium silicate and calcium hydroxide with a mass ratio of 1:3-5 is added as an inhibitor; in the roughing stage, a mixture of thiocyanate and allyl thiocarbamate with a mass ratio of 3-5:1 is added as a collector; in the cleaning stage, a mixture of sodium silicate and calcium hydroxide with a mass ratio of 1:3-5 is added as an inhibitor; and in the scavenging stage, a mixture of thiocyanate and allyl thiocarbamate with a mass ratio of 3-5:1 is added as a collector.

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