Beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ore

Abstract

The invention provides a beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ore. The beneficiation method comprises the steps of rough grinding, copper-silver optimal flotation, zinc-sulfur mixed flotation, classification, concentration, ore grinding, zinc-sulfur separation, shaking table reselection, middling regrinding, flotation desulfurization, copper-silver-sulfur separation and the like. Aiming at the characteristics of coarse cassiterite inlaying and fine and non-uniform sulphide ore inlaying, the problem that sulphide ore and cassiterite in tin polymetallic ore are difficult to recover at the same time is solved through the processes of quality classification, stage grinding and centralized treatment. According to the method, the tin recovery rate is guaranteed, meanwhile, copper and silver which are wide and fine in disseminated particle size are recovered in a segmented mode, the grade of the zinc concentrate is improved, efficient comprehensive recovery of valuable metal such as tin, silver, copper and zinc is achieved, the resource economic benefits are maximized, and the problems of excessive grinding of tin and loss of copper and silver are effectively solved.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral beneficiation and processing, and in particular relates to a beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores. Background Art

[0002] Tin is an important metal resource, widely used in electronics, chemical industry 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 reduction of high-grade single tin ore resources, associated tin ores have gradually become the main source of tin. Among them, the development and utilization of tin-associated polymetallic ores has become an important direction of current mineral resource development. However, compared with single tin ores, the development of such deposits faces higher technical difficulties, especially in the mineral processing technology, where there are significant challenges.

[0003] In the prior art, the recovery of cassiterite mainly depends on the gravity separation process. For example, patent CN102658236B proposes a method to re-select and recycle the classified fine mud cassiterite minerals through a fine mud shaker to obtain fine mud cassiterite rough concentrates of different particle sizes. Similarly, patent CN115814934A describes a process in which the tailings slurry is stirred evenly and then fed into a hydraulic classification box. The fine sand and mud ore separated by the hydraulic classification box enter the fine sand shaker and grooved shaker driven by a linear motor for separation, and finally produce tin rough concentrate, tin medium ore and tin tailings. The main separation process of cassiterite is gravity separation, but in polymetallic sulfide ores, the density of sulfide minerals is relatively large (generally >4g / cm 3 ), and cassiterite density (6.95 g / cm 3 ) is relatively small, which interferes with the cassiterite reselection effect. In addition, the sulfide ore has good floatability, which further interferes with the separation of cassiterite during the flotation of fine-grained cassiterite. This interference not only leads to a low tin recovery rate, but also causes more sulfide minerals to be doped in the tin concentrate, reducing the grade and value of the tin concentrate.

[0004] In addition, polymetallic sulfide ores often contain valuable metal resources such as copper, silver, and zinc, and the value of these metal resources accounts for a high proportion of the total value of the mineral, especially in low-grade tin ores, where the metal value in sulfide ores may account for more than 50%. In existing technologies, sulfide minerals are often removed without being effectively recovered, resulting in serious waste of resources.

[0005] The mineralization characteristics of this type of deposits lead to significant differences in the particle size of cassiterite and sulfide minerals. Cassiterite is coarsely embedded, while sulfide minerals (such as chalcopyrite, pyrite, sphalerite, etc.) are finely embedded. In actual production, the grinding fineness is usually based on cassiterite recovery, while taking into account the recovery of sulfide ores. However, insufficient grinding dissociation makes it impossible to efficiently recover valuable metals such as copper and silver. Some copper and silver resources enter zinc concentrate, sulfide concentrate and cassiterite desulfurization products, which not only causes a waste of copper and silver resources, but also has a negative impact on 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 effective recovery of cassiterite has become a key technical issue in improving the efficiency of tin concentrators. Summary of the invention

[0007] The purpose of the present invention is to provide a beneficiation method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ore, in view of the fact that copper and silver cannot be efficiently recovered in the current tin concentrator, there are problems such as waste of copper and silver resources, excessive impurity content in zinc concentrate, and high copper and silver content in sulfur concentrate, so as to achieve efficient recovery of tin in tin-copper-silver-zinc polymetallic ore, reduce the silver-copper occupancy rate in zinc concentrate and sulfur concentrate, improve the recovery rate of copper and silver, and reduce the impurity content in zinc concentrate, so as to finally achieve efficient utilization of resources.

[0008] The technical solution adopted by the present invention is as follows:

[0009] A method for recovering copper and silver from a complex tin-silver-copper-zinc polymetallic ore comprises the following steps:

[0010] S1, rough grinding the raw ore, and then grinding after slurry adjustment to obtain grinding products;

[0011] S2, subjecting the grinding product obtained in S1 to copper-silver flotation, wherein the copper-silver flotation process includes adding a collector for roughing, adding an inhibitor for concentrating and scavenging, and obtaining a silver-copper concentrate 1 and a silver-copper tailings;

[0012] S3, subjecting the silver-copper tailings obtained in S2 to zinc-sulfur mixed flotation, wherein the zinc-sulfur mixed flotation process comprises adding an activator and a collector for roughing and concentrating, and adding a collector for scavenging to obtain zinc-sulfur mixed flotation concentrate and zinc-sulfur mixed flotation tailings;

[0013] S4, classifying the zinc-sulfur mixed flotation concentrate obtained in S3 to obtain a coarse particle product and a fine particle product, and grinding the fine particle product to obtain a ground product;

[0014] S5, the grinding product obtained in S4 is subjected to de-drug scrubbing and then enters the zinc-sulfur separation operation, and the zinc-sulfur separation process includes adding an inhibitor and a collector for roughing, adding an inhibitor for fine selection, and adding a collector for scavenging to obtain zinc concentrate and sulfur concentrate 1;

[0015] S6, the zinc-sulfur mixed flotation tailings obtained in S3 are put into a shaking table for gravity separation to obtain a shaking table concentrate, a shaking table intermediate ore and a shaking table tailings, and the shaking table intermediate ore is ground to obtain a grinding product;

[0016] S7, the grinding product obtained in S6 enters the flotation desulfurization operation, and the flotation desulfurization process includes adding a collector for roughing, concentrating and scavenging to obtain sulfur concentrate 2 and desulfurized tailings;

[0017] S8. The sulfur concentrate 1 obtained from S5 and the sulfur concentrate 2 obtained from S7 are subjected to copper-silver-sulfur flotation after being scrubbed and de-doped. The copper-silver-sulfur flotation process comprises adding inhibitors and collectors for roughing, adding inhibitors for fine selection, and adding collectors for scavenging to obtain silver-copper concentrate 2 and sulfur concentrate.

[0018] In view of the problem of poor recovery of copper, silver and zinc, the concepts of coarse particle selection, stage grinding and quality classification recovery are proposed. In the main process of tin selection, coarse particle selection is adopted to prevent over-grinding of cassiterite, follow the principle of early recovery, and ensure efficient recovery of tin. For tin medium ore with insufficient dissociation degree, re-grinding and desulfurization are carried out, which not only realizes the recovery of dissociated sulfide ore, but also further dissociates tin, so as to achieve step-by-step separation and enrichment of tin and sulfur; in the branch process or the process after tin selection, copper and silver are further ground to separate from zinc, sulfur or gangue minerals, and finally realize the recovery of copper, zinc and silver. Finally, the process of "coarse grinding-copper and silver flotation-zinc and sulfur mixed flotation-classification-coarse particle return and re-grinding-fine particle zinc and sulfur separation-sulfur concentrate re-grinding and re-selection of copper and silver-cassiterite shaking table re-selection" is adopted, and high-efficiency reagents are used in the flotation process to achieve effective separation of copper, silver, zinc and sulfur, and at the same time achieve efficient recovery of tin in copper, silver and zinc polymetallic ores. It 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] Furthermore, the grinding concentration in step S1 is 65-85%, and the mass of particles with a particle size smaller than 0.074 mm in the grinding product accounts for 45-60% of the total particle mass.

[0020] Furthermore, in step S2, the collector is a mixture of thiocyanate and allylthiocarbamate isobutyl ester 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 the sodium-containing compound A is sodium sulfide or sodium hydrosulfide, and the sodium compound B is sodium carbonate or sodium sulfite.

[0021] Thiocyanate and allylthiocarbamate isobutyl ester are highly efficient collectors for copper and silver respectively, and the two can play a synergistic and complementary role in the recovery of silver-containing copper minerals, promoting the capture effect of copper and silver. If only one of them is used, the recovery rate of copper and silver will be reduced.

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

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

[0024] Furthermore, in the grinding product of step S4, the mass of particles with a size smaller than 0.043 mm accounts for 75-85% of the mass of the total particles.

[0025] Furthermore, in step S5, the drug removal scrubbing is: adding coconut shell activated carbon or fruit shell activated carbon as a drug removal agent for drug removal scrubbing, and the scrubbing time is 0.5-1h; 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, and in the roughing stage, a mixture of ethylthiocarbamate, α-terpene alcohol and dithiocarbamate in a mass ratio of 2-3:1:2-3 is added as a collector, in the fine selection 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 ethylthiocarbamate, 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 to allow the agents to interact more efficiently with mineral particles, reducing non-target minerals such as gangue and pyrite that float up due to entrainment or agglomeration; the three agents of ethiocarbamate, α-terpene alcohol and dithiocarbamate act synergistically. Ethiocarbamate and dithiocarbamate form different types of covalent bonds with the surface of sphalerite to enhance the capture effect on minerals, while α-terpene alcohol can produce fine foam, which strengthens the connection between mineral particles and foam, thereby forming a stable bridging structure between the collector and the mineral.

[0027] Furthermore, in step S6, the mass of particles with a particle size smaller than 0.074 mm in the ground ore product accounts for 80-90% of the total particle mass.

[0028] Furthermore, the collector in step S7 is sodium dihydroxymethyl propanedixanthate or isopentyl xanthate.

[0029] Further, in step S8, the drug removal scrubbing is: adding coconut shell activated carbon or fruit shell activated carbon as a drug removal agent for drug removal scrubbing, and the scrubbing time is 1.5-2h; 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, and in the roughing stage, a mixture of thiocyanate and allylthiocarbamate isobutyl ester in a mass ratio of 3-5:1 is added as a collector, in the fine selection 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 allylthiocarbamate isobutyl ester in a mass ratio of 3-5:1 is added as a collector.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The copper and silver recovery rate has been significantly improved, and the efficiency of the concentrator has been significantly increased;

[0032] (2) The copper and sulfur grades in zinc concentrate were significantly reduced, and the zinc grade in zinc concentrate was significantly increased;

[0033] (3) The valuable metal content in the sulfur concentrate is significantly reduced, and the sulfur concentrate can be sold directly or backfilled without the need for storage and further processing;

[0034] (4) The coarse particles of zinc-sulfur mixed flotation concentrate are returned to the previous grinding mill and do not need to be ground separately, thus reducing the number of grinding mills and the grinding process;

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

[0036] (6) With the main process, grinding fineness and tin separation technology unchanged, only classification and regrinding and re-separation of sulfur concentrate are added, which is conducive to the technical transformation of the same type of concentrators;

[0037] (7) It can improve the current problem of low recovery rate of associated sulfide ores in tin mines and achieve simultaneous and efficient enrichment of tin, copper, silver and zinc. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is an operation flow chart of the present invention. DETAILED DESCRIPTION

[0039] The present invention is further described below in conjunction with examples. These examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually carried out according to conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as conventional markets. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of protection claimed by the present invention.

[0040] Example 1

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

[0042] (1) Water was added to the raw ore to adjust the slurry concentration to 75%, and then 1000 g / t of zinc hydroxide was added to grind the ore so that the mass of particles smaller than 0.074 mm accounted for 50% of the total mass of particles, thereby obtaining a grinding product 1.

[0043] (2) The grinding product 1 was subjected to copper and silver flotation. 30 g / t of collector (the mass ratio of thiocyanate: allylthiocarbamate isobutyl ester was 3:1) was added to the grinding product 1. After a roughing operation, a roughing concentrate and a roughing tailing were obtained. 300 g / t of inhibitor (the mass ratio of sodium sulfide: sodium carbonate: zinc sulfate was 1:3:6) was added to the roughing concentrate. After the first concentration, a concentrated 1 concentrate and a concentrated 1 tailing were obtained. 100g / t of inhibitor (the mass ratio of sodium sulfide: sodium carbonate: zinc sulfate is 1:3:6) is added, and after the second concentration, the concentrated 2 concentrate and the concentrated 2 tailings are obtained. 8g / t of collector (the mass ratio of thiocyanate: allylthiocarbamic acid isobutyl ester is 3:1) is added to the roughing tailings, and after a scavenging, the scavenging concentrate and scavenging tailings are obtained; the scavenging concentrate and the concentrated 1 tailings are returned to the roughing operation, and the concentrated 2 tailings are returned to the first concentration operation. The final concentrated 2 concentrate is the silver-copper concentrate 1, and the scavenging tailings are the silver-copper tailings.

[0044] (3) The silver-copper tailings are subjected to zinc-sulfur mixed flotation operation. 100 g / t of activator (copper sulfate) and 80 g / t of collector (sodium dihydroxymethyl propanediol xanthate) are added to the silver-copper tailings. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 20 g / t of collector (sodium dihydroxymethyl propanediol xanthate) is added to the roughing tailings. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the scavenging tailings are returned to the roughing operation. The final concentrated concentrate is a zinc-sulfur mixed flotation concentrate, and the scavenging tailings are zinc-sulfur mixed flotation tailings.

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

[0046] (5) The coarse particle product is placed in a concentration device for concentration to obtain concentrated underflow and overflow water. The concentration of the concentrated underflow is adjusted to reach a target concentration of 60%, and the concentrated underflow is returned to the coarse grinding operation of S1.

[0047] (6) The fine particle product is placed in a grinding machine for grinding, so that the mass of particles smaller than 0.043 mm accounts for 75% of the total particle mass, thereby obtaining a ground product 2.

[0048] (7) The grinding product 2 is subjected to zinc-sulfur separation. After adding coconut shell activated carbon to the grinding product 2 for de-drugging and scrubbing for 0.5 h, 600 g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide is 1:3) and 10 g / t of collector (the mass ratio of ethionamide to α-terpene alcohol to dithiocarbamate is 2:1:2) are added. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 300 g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide is 1:3) is added to the roughing concentrate. After the first concentration, a concentrated 1 concentrate and a concentrated 1 tailing are obtained. 200 g / t of inhibitor (silicon dioxide) is added to the concentrated 1 concentrate. The mass ratio of sodium silicate: calcium hydroxide is 1:3), after the second concentration, the concentrated 2 concentrate and the concentrated 2 tailings are obtained, 200g / t of inhibitor is added to the concentrated 2 concentrate (the mass ratio of sodium silicate: calcium hydroxide is 1:3), after the third concentration, the concentrated 3 concentrate and the concentrated 3 tailings are obtained, 2g / t of collector is added to the roughing tailings (the mass ratio of ethylthiocarbamate: α-terpene alcohol: dithiocarbamate is 2:1:2), after one scavenging, the scavenging concentrate and the scavenging tailings are obtained; the scavenging concentrate and the concentrated 1 tailings are returned to the roughing operation, the concentrated 2 tailings are returned to the first concentration operation, and the concentrated 3 tailings are returned to the second concentration operation. The finally obtained concentrated 3 concentrate is zinc concentrate (zinc-silver concentrate), and the scavenging tailings are sulfur concentrate 1.

[0049] (8) The zinc-sulfur mixed flotation tailings are placed in a shaking table device 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 placed in a grinding machine for grinding, so that the mass of particles smaller than 0.074 mm accounts for 90% of the total mass of particles, thereby obtaining a grinding product 3.

[0051] (10) The grinding product 3 is subjected to flotation desulfurization operation. 40 g / t of collector (butyl xanthate) is added to the grinding product 3. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 10 g / t of collector (butyl xanthate) is added to the roughing tailing. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the scavenging tailing are returned to the roughing operation. The final concentrated concentrate is the sulfur concentrate 2, and the scavenging tailing is the desulfurization tailing. The desulfurization tailing is returned to the shaking table re-selection operation.

[0052] (11) Sulfur concentrate 1 and sulfur concentrate 2 were subjected to copper, silver and sulfur flotation. After adding fruit shell activated carbon to sulfur concentrate 1 and sulfur concentrate 2 for de-doping and scrubbing for 1 hour, 800 g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide was 1:3) and 50 g / t of collector (the mass ratio of thiocyanate to allylthiocarbamate isobutyl ester was 3:1) were added. After one roughing, roughing concentrate and roughing tailings were obtained. 400 g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide was 1:3) was added to the roughing concentrate. After the first concentration, concentrated 1 concentrate and concentrated 1 tailings were obtained. 200 g / t of inhibitor was added to the concentrated 1 concentrate. The first step is to add a 100g / t inhibitor (the mass ratio of sodium silicate to calcium hydroxide is 1:3) to the second concentration to obtain the selected 2 concentrate and the selected 2 tailings. The selected 2 concentrate is added with 100g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide is 1:3). After the third concentration, the selected 3 concentrate and the selected 3 tailings are obtained. The roughing tailings are added with 10g / t of collector (the mass ratio of thiocyanate to allylthiocarbamic acid isobutyl ester is 3:1). After one scavenging, the scavenging concentrate and the scavenging tailings are obtained. The scavenging concentrate and the selected 1 tailings are returned to the roughing operation, the selected 2 tailings are returned to the first concentration operation, and the selected 3 tailings are returned to the second concentration operation. The selected 3 concentrate finally obtained is the silver-copper concentrate 2, and the scavenging tailings are the sulfur concentrate.

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

[0054] Example 2

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

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

[0057] (2) The grinding product 1 was subjected to copper and silver flotation. 40 g / t of collector (the mass ratio of thiocyanate to isobutyl allylthiocarbamate was 5:1) was added to the grinding product 1. After a roughing operation, a roughing concentrate and a roughing tailing 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 concentration, a concentrated 1 concentrate and a concentrated 1 tailing were obtained. 50g / t of inhibitor (sodium sulfide: sodium sulfite: zinc sulfate = 1:3:6) was added, and after the second concentration, the concentrated 2 concentrate and the concentrated 2 tailings were obtained. 10g / t of collector (the mass ratio of thiocyanate: allylthiocarbamic acid isobutyl ester was 5:1) was added to the roughing tailings, and after a scavenging, the scavenging concentrate and scavenging tailings were obtained; the scavenging concentrate and the concentrated 1 tailings were returned to the roughing operation, and the concentrated 2 tailings were returned to the first concentration operation. The final concentrated 2 concentrate was silver-copper concentrate 1, and the scavenging tailings were silver-copper tailings.

[0058] (3) The silver-copper tailings are subjected to zinc-sulfur mixed flotation operation. 80 g / t of activator (copper chloride) and 60 g / t of collector (sodium dihydroxymethyl propanediol xanthate) are added to the silver-copper tailings. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 20 g / t of collector (sodium dihydroxymethyl propanediol xanthate) is added to the roughing tailings. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the scavenging tailings are returned to the roughing operation. The final concentrated concentrate is a zinc-sulfur mixed flotation concentrate, and the scavenging tailings are zinc-sulfur mixed flotation tailings.

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

[0060] (5) The coarse particle product is placed in a concentration device for concentration to obtain concentrated underflow and overflow water. The concentration of the concentrated underflow is adjusted to reach a target concentration of 60%, and the concentrated underflow is returned to the coarse grinding operation of S1.

[0061] (6) The fine particle product is placed in a grinding machine for grinding, so that the mass of particles smaller than 0.043 mm accounts for 85% of the total particle mass, thereby obtaining a ground product 2.

[0062] (7) The grinding product 2 is subjected to zinc-sulfur separation. Coconut shell activated carbon is added to the grinding product 2 for de-drug scrubbing for 1 hour, and then 500 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) and 8 g / t of collector (ethionamide: α-terpene alcohol: dithiocarbamate = 3:1:3) are added. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 200 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) is added to the roughing concentrate. After the first concentration, a concentrated 1 concentrate and a concentrated 1 tailing are obtained. 100 g / t of inhibitor (sodium silicate) is added to the concentrated 1 concentrate. : calcium hydroxide = 1:5), after the second concentration, concentrated 2 concentrate and concentrated 2 tailings are obtained, 100g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) is added to the concentrated 2 concentrate, after the third concentration, concentrated 3 concentrate and concentrated 3 tailings are obtained, 2g / t of collector (ethylthiocarbamate: α-terpene alcohol: dithiocarbamate = 3:1:3) is added to the roughing tailings, after one scavenging, scavenging concentrate and scavenging tailings are obtained; the scavenging concentrate and concentrated 1 tailings are returned to the roughing operation, the concentrated 2 tailings are returned to the first concentration operation, and the concentrated 3 tailings are returned to the second concentration operation. The final concentrated 3 concentrate is zinc concentrate (zinc-silver concentrate), and the scavenging tailings are sulfur concentrate 1.

[0063] (8) The zinc-sulfur mixed flotation tailings are placed in a shaking table device 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 placed in a grinding machine for grinding, so that the mass of particles smaller than 0.074 mm accounts for 80% of the total mass of particles, thereby obtaining a grinding product 3.

[0065] (10) The grinding product 3 is subjected to flotation desulfurization. 30 g / t of collector (butyl xanthate) is added to the grinding product 3. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blanking operation to obtain a concentrated concentrate and a concentrated tailing. 10 g / t of collector (butyl xanthate) is added to the roughing tailing. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the scavenging tailing are returned to the roughing operation. The final concentrated concentrate is the sulfur concentrate 2, and the scavenging tailing is the desulfurization tailing. The desulfurization tailing is returned to the shaking table re-selection operation.

[0066] (11) Sulfur concentrate 1 and sulfur concentrate 2 were subjected to copper, silver and sulfur flotation. After adding fruit shell activated carbon to sulfur concentrate 1 and sulfur concentrate 2 for de-doping and scrubbing for 1.5 hours, 600 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) and 40 g / t of collector (thiocyanate: allylthiocarbamate isobutyl ester = 5:1) were added. After one roughing, roughing concentrate and roughing tailings were obtained. 300 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) was added to the roughing concentrate. After the first cleaning, concentrator 1 concentrate and concentrator 1 tailings were obtained. 150 g / t of The inhibitor (sodium silicate: calcium hydroxide = 1:5) was added to the concentrate 2 and the tailings 2 were obtained after the second concentration. 100g / t of inhibitor (sodium silicate: calcium hydroxide = 1:5) was added to the concentrate 2. After the third concentration, the concentrate 3 and tailings 3 were obtained. 8g / t of collector (sulfur nitrogen nitrile ester: allyl thiocarbamic acid isobutyl ester = 5:1) was added to the roughing tailings. After one scavenging, the scavenging concentrate and tailings were obtained. The scavenging concentrate and tailings 1 were returned to the roughing operation, the tailings 2 were returned to the first concentration operation, and the tailings 3 were returned to the second concentration operation. The final concentrate 3 was silver-copper concentrate 2, and the scavenging tailings were sulfur concentrate.

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

[0068] Example 3

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

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

[0071] (2) The grinding product 1 is subjected to copper and silver flotation. 40 g / t of collector (sulfuryl nitrile ester: allyl thiocarbamate isobutyl ester = 3:1) is added to the grinding product 1. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 300 g / t of inhibitor (sodium hydrosulfide: sodium carbonate: zinc sulfate = 1:5:10) is added to the roughing concentrate. After the first cleaning operation, a cleaning 1 concentrate and a cleaning 1 tailing are obtained. 100g / t of inhibitor (sodium hydrosulfide: sodium carbonate: zinc sulfate = 1:5:10) was added, and after the second concentration, the concentrated 2 concentrate and the concentrated 2 tailings were obtained. 10g / t of collector (sulfurization nitrogen ester: allyl thiocarbamic acid isobutyl ester = 3:1) was added to the roughing tailings, and after a scavenging, the scavenging concentrate and scavenging tailings were obtained; the scavenging concentrate and the concentrated 1 tailings were returned to the roughing operation, and the concentrated 2 tailings were returned to the first concentration operation. The final concentrated 2 concentrate is the silver-copper concentrate 1, and the scavenging tailings are the silver-copper tailings.

[0072] (3) The silver-copper tailings are subjected to zinc-sulfur mixed flotation operation, 100 g / t of activator (copper sulfate) and 70 g / t of collector (isoamyl xanthate) are added to the silver-copper tailings, and a roughing concentrate and a roughing tailing are obtained after a roughing operation. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 15 g / t of collector (isoamyl xanthate) is added to the roughing tailings, and a scavenging operation is performed to obtain a scavenging concentrate and a scavenging tailing; the scavenging concentrate and the scavenging tailing are returned to the roughing operation. The final concentrated concentrate is a zinc-sulfur mixed flotation concentrate, and the scavenging tailings are a zinc-sulfur mixed flotation tailing.

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

[0074] (5) The coarse particle product is placed in a concentration device for concentration to obtain concentrated underflow and overflow water. The concentration of the concentrated underflow is adjusted to reach a target concentration of 70%, and the concentrated underflow is returned to the coarse grinding operation of S1.

[0075] (6) The fine particle product is placed in a grinding machine for grinding, so that the mass of particles smaller than 0.043 mm accounts for 80% of the total particle mass, thereby obtaining a ground product 2.

[0076] (7) The grinding product 2 is subjected to zinc-sulfur separation. After adding coconut shell activated carbon to the grinding product 2 for de-drug scrubbing for 1 hour, 600 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) and 12 g / t of collector (ethionamide: α-terpene alcohol: dithiocarbamate = 3:1:3) are added. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 200 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) is added to the roughing concentrate. After the first concentration, a concentrated 1 concentrate and a concentrated 1 tailing are obtained. 100 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) is added to the concentrated 1 concentrate. The first step is to select the selected ore and tailings of the selected ore. The first step is to select the selected ore and tailings of the selected ore. The second step is to select the selected ore and tailings of the selected ore. The first step is to select the selected ore and tailings of the selected ore. The second step is to select the selected ore and tailings of the selected ore. The second step is to select the selected ore and tailings of the selected ore. The second step is to select the selected ore and tailings of the selected ore. The second step is to select the selected ore and tailings of the selected ore. The selected ore and tailings of the selected ore are returned to the roughing operation, the selected ore and tailings of the selected ore are returned to the first selection operation, and the selected ore and tailings of the selected ore are returned to the second selection operation. The selected ore and tailings of the selected ore are finally zinc concentrate (zinc-silver concentrate), and the scavenging tailings are sulfur concentrate 1.

[0077] (8) The zinc-sulfur mixed flotation tailings are placed in a shaking table device 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 placed in a grinding machine for grinding, so that the mass of particles smaller than 0.074 mm accounts for 90% of the total mass of particles, thereby obtaining a grinding product 3.

[0079] (10) The grinding product 3 is subjected to flotation desulfurization operation. 40 g / t of collector (butyl xanthate) is added to the grinding product 3. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 10 g / t of collector (butyl xanthate) is added to the roughing tailing. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the scavenging tailing are returned to the roughing operation. The final concentrated concentrate is the sulfur concentrate 2, and the scavenging tailing is the desulfurization tailing. The desulfurization tailing is returned to the shaking table re-selection operation.

[0080] (11) Sulfur concentrate 1 and sulfur concentrate 2 were subjected to copper, silver and sulfur flotation. After adding fruit shell activated carbon to sulfur concentrate 1 and sulfur concentrate 2 for de-doping and scrubbing for 2 hours, 800 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) and 30 g / t of collector (thiocyanate: allylthiocarbamate isobutyl ester = 3:1) were added. After a roughing operation, a roughing concentrate and a roughing tailing were obtained. 500 g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) was added to the roughing concentrate. After the first concentration, a concentrated 1 concentrate and a concentrated 1 tailing were obtained. 300 g / t of inhibitor was added to the concentrated 1 concentrate. Preparation (sodium silicate: calcium hydroxide = 1:3), after the second concentration, concentrated 2 concentrate and concentrated 2 tailings are obtained, 200g / t of inhibitor (sodium silicate: calcium hydroxide = 1:3) is added to the concentrated 2 concentrate, after the third concentration, concentrated 3 concentrate and concentrated 3 tailings are obtained, 8g / t of collector (sulfur nitrogen nitrile ester: allyl thiocarbamic acid isobutyl ester = 3:1) is added to the roughing tailings, after one scavenging, scavenging concentrate and scavenging tailings are obtained; the scavenging concentrate and concentrated 1 tailings are returned to the roughing operation, the concentrated 2 tailings are returned to the first concentration operation, and the concentrated 3 tailings are returned to the second concentration operation. The final concentrated 3 concentrate is silver-copper concentrate 2, and the scavenging tailings are sulfur concentrate.

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

[0082] Comparative Example 1

[0083] The sample selected is the same sample as that in Example 1, namely, the Gejiu tin-copper-zinc polymetallic ore in Yunnan, wherein 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%.

[0084] The copper, silver and zinc are recovered by conventional process and conventional reagent system. The specific steps are as follows:

[0085] (1) Water is added to the raw ore to adjust the slurry concentration to 75%, and the ore is ground until the mass of particles smaller than 0.074 mm accounts for 50% of the total mass of particles, thereby obtaining a ground ore product 1.

[0086] (2) The grinding product 1 is subjected to copper and silver flotation operation. 800 g / t of inhibitor (sodium carbonate: zinc sulfate in a mass ratio of 1:2) and 30 g / t of collector (sulfuryl nitrile ester) are added to the grinding product. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 300 g / t of inhibitor (sodium carbonate: zinc sulfate in a mass ratio of 1:2) are added to the roughing concentrate. After a first cleaning operation, a cleaning 1 concentrate and a cleaning 1 tailing are obtained. 100 g / t of inhibitor (sodium carbonate: zinc sulfate in a mass ratio of 1:2) are added to the roughing concentrate. After a second cleaning operation, a cleaning 2 concentrate and a cleaning 2 tailing are obtained. 8 g / t of collector (sulfuryl nitrile ester) is added to the roughing tailing. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the cleaning 1 tailing are returned to the roughing operation, and the cleaning 2 tailing is returned to the first cleaning operation. The final concentrated ore is silver-copper concentrate, and the scavenged tailings are silver-copper tailings.

[0087] (3) The silver-copper tailings are subjected to zinc-sulfur mixed flotation operation. 100 g / t of activator (copper sulfate) and 80 g / t of collector (butyl xanthate) are added to the silver-copper tailings. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 20 g / t of collector (butyl xanthate) is added to the roughing tailings. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the concentrated tailing are returned to the roughing operation. The final concentrated concentrate is a zinc-sulfur mixed flotation concentrate, and the scavenging tailing is a zinc-sulfur mixed flotation tailing.

[0088] (4) The zinc-sulfur mixed flotation concentrate is directly subjected to zinc-sulfur separation operation. The mixed flotation concentrate is ground until the mass of particles with a size less than 0.043 mm accounts for 75% of the total particle mass to obtain grinding product 2. Coconut shell activated carbon is added to the grinding product 2 for de-drug scrubbing for 1 hour, and then 1000 g / t of inhibitor (lime) and 12 g / t of collector (ethionamide) are added. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 200 g / t of inhibitor (lime) is added to the roughing concentrate. After a first concentration, a concentration 1 concentrate and a concentration 1 tailing are obtained. , add 100g / t of depressant (lime) to the selected 1 concentrate, after the second selection, obtain the selected 2 concentrate and the selected 2 tailings, add 100g / t of depressant (lime) to the selected 2 concentrate, after the third selection, obtain the selected 3 concentrate and the selected 3 tailings, add 2g / t of collector (ethiocarbamate) to the rougher tailings, after one scavenging, obtain the scavenging concentrate and the scavenging tailings; the scavenging concentrate and the selected 1 tailings are returned to the rougher operation, the selected 2 tailings are returned to the first selection operation, and the selected 3 tailings are returned to the second selection operation. The selected 3 concentrate finally obtained is a zinc-silver concentrate, and the scavenging tailings are a sulfur concentrate.

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

[0090] Comparative Example 2

[0091] The sample selected is the same sample as that in Example 1, namely, the Gejiu tin-copper-zinc polymetallic ore in Yunnan, wherein 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%.

[0092] The copper, silver and zinc are recovered by using conventional process and the new reagent system of Example 1, and the specific steps are as follows:

[0093] (1) Water is added 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 mass of particles, thereby obtaining a grinding product 1.

[0094] (2) The milled product 1 was subjected to a copper and silver flotation operation. 30 g / t of a collector (the mass ratio of thiocyanate: allylthiocarbamate isobutyl ester was 3:1) was added to the milled product. After a roughing operation, a roughing concentrate and a roughing tailing were obtained. 300 g / t of an inhibitor (the mass ratio of sodium sulfide: sodium carbonate: zinc sulfate was 1:3:6) was added to the roughing concentrate. After a first concentration operation, a concentrated 1 concentrate and a concentrated 1 tailing were obtained. 100g / t of inhibitor (the mass ratio of sodium sulfide: sodium carbonate: zinc sulfate is 1:3:6) is added, and after the second concentration, the concentrated 2 concentrate and the concentrated 2 tailings are obtained. 8g / t of collector (the mass ratio of thiocyanate: allylthiocarbamate isobutyl ester is 3:1) is added to the roughing tailings, and after a scavenging, the scavenging concentrate and scavenging tailings are obtained; the scavenging concentrate and the concentrated 1 tailings are returned to the roughing operation, and the concentrated 2 tailings are returned to the first concentration operation. The final concentrated 2 concentrate is a silver-copper concentrate, and the scavenging tailings are silver-copper tailings.

[0095] (3) The silver-copper tailings are subjected to zinc-sulfur mixed flotation operation. 100 g / t of activator (copper sulfate) and 80 g / t of collector (sodium dihydroxymethyl propanediol xanthate) are added to the silver-copper tailings. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 20 g / t of collector (sodium dihydroxymethyl propanediol xanthate) is added to the roughing tailings. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the scavenging tailings are returned to the roughing operation. The final concentrated concentrate is a zinc-sulfur mixed flotation concentrate, and the scavenging tailings are zinc-sulfur mixed flotation tailings.

[0096] (4) The zinc-sulfur mixed flotation concentrate is subjected to zinc-sulfur separation operation. The mixed flotation concentrate is ground until the mass of particles with a size less than 0.043 mm accounts for 75% of the total mass of particles to obtain grinding product 2. Coconut shell activated carbon is added to the grinding product 2 for de-medication and scrubbing for 0.5 h, and then 600 g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide is 1:3) and 10 g / t of collector (the mass ratio of ethiocarbamate to α-terpene alcohol to dithiocarbamate is 2:1:2) are added. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 300 g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide is 1:3) is added to the roughing concentrate. After the first concentration, a concentrated 1 concentrate and a concentrated 1 tailing are obtained. Add 200g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide is 1:3) to the selected 1 concentrate, and after the second selection, obtain the selected 2 concentrate and the selected 2 tailings. Add 200g / t of inhibitor (the mass ratio of sodium silicate to calcium hydroxide is 1:3) to the selected 2 concentrate, and after the third selection, obtain the selected 3 concentrate and the selected 3 tailings. Add 2g / t of collector (the mass ratio of ethiocarbamate: α-terpene alcohol: dithiocarbamate is 2:1:2) to the roughing tailings, and after one scavenging, obtain the scavenging concentrate and scavenging tailings; the scavenging concentrate and the selected 1 tailings are returned to the roughing operation, the selected 2 tailings are returned to the first selection operation, and the selected 3 tailings are returned to the second selection operation. The selected 3 concentrate finally obtained is a zinc concentrate (zinc-silver concentrate), and the scavenging tailings are a sulfur concentrate.

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

[0098] Comparative Example 3

[0099] The sample selected is the same sample as that in Example 1, namely, the Gejiu tin-copper-zinc polymetallic ore in Yunnan, wherein 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%.

[0100] The copper, silver and zinc are recovered by using the new process method of Example 1 and the conventional reagent system, and the specific steps are as follows:

[0101] (1) Water was added to the raw ore to adjust the slurry concentration to 75%, and then 1000 g / t of zinc hydroxide was added to grind the ore so that the mass of particles smaller than 0.074 mm accounted for 50% of the total mass of particles, thereby obtaining a grinding product 1.

[0102] (2) The grinding product 1 is subjected to copper and silver flotation. 30 g / t of collector (sulfuryl nitrile ester) is added to the grinding product 1. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 300 g / t of inhibitor (the mass ratio of sodium carbonate to zinc sulfate is 1:2) is added to the roughing concentrate. After the first cleaning operation, a concentrated 1 concentrate and a concentrated 1 tailing are obtained. 100 g / t of inhibitor (the mass ratio of sodium carbonate to zinc sulfate is 1:2) is added to the roughing concentrate. After a second cleaning operation, a concentrated 2 concentrate and a concentrated 2 tailing are obtained. 8 g / t of collector (sulfuryl nitrile ester) is added to the roughing tailing. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the concentrated 1 tailing are returned to the roughing operation, and the concentrated 2 tailing is returned to the first cleaning operation. The finally obtained concentrated 2 concentrate is a silver-copper concentrate 1, and the scavenging tailing is a silver-copper tailing.

[0103] (3) The silver-copper tailings are subjected to zinc-sulfur mixed flotation operation. 100 g / t of activator (copper sulfate) and 80 g / t of collector (butyl xanthate) are added to the silver-copper tailings. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 20 g / t of collector (butyl xanthate) is added to the roughing tailings. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the concentrated tailing are returned to the roughing operation. The final concentrated concentrate is a zinc-sulfur mixed flotation concentrate, and the scavenging tailing is a zinc-sulfur mixed flotation tailing.

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

[0105] (5) The coarse particle product is placed in a concentration device for concentration to obtain concentrated underflow and overflow water. The concentration of the concentrated underflow is adjusted to reach a target concentration of 60%, and the concentrated underflow is returned to the coarse grinding operation in step 1.

[0106] (6) The fine particle product is placed in a grinding machine for grinding, so that the mass of particles smaller than 0.043 mm accounts for 75% of the total particle mass, thereby obtaining a ground product 2.

[0107] (7) The grinding product 2 is subjected to zinc-sulfur separation. Coconut shell activated carbon is added to the grinding product 2 for de-drug scrubbing for 0.5 h, and then 600 g / t of an inhibitor (lime) and 10 g / t of a collector (butyl xanthate) are added. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. 300 g / t of an inhibitor (lime) is added to the roughing concentrate. After the first concentration, a concentrated 1 concentrate and a concentrated 1 tailing are obtained. 200 g / t of an inhibitor (lime) is added to the concentrated 1 concentrate. After the second concentration, concentrated 2 concentrate and concentrated 2 tailings are obtained. 200g / t of depressant (lime) is added to the concentrated 2 concentrate. After the third concentration, concentrated 3 concentrate and concentrated 3 tailings are obtained. 2g / t of collector (butyl xanthate) is added to the roughing tailings. After one scavenging, scavenging concentrate and scavenging tailings are obtained; the scavenging concentrate and concentrated 1 tailings are returned to the roughing operation, the concentrated 2 tailings are returned to the first concentration operation, and the concentrated 3 tailings are returned to the second concentration operation. The final concentrated 3 concentrate is zinc concentrate (zinc-silver concentrate), and the scavenging tailings are sulfur concentrate 1.

[0108] (8) The zinc-sulfur mixed flotation tailings are placed in a shaking table device 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 placed in a grinding machine for grinding, so that the mass of particles smaller than 0.074 mm accounts for 90% of the total mass of particles, thereby obtaining a grinding product 3.

[0110] (10) The grinding product 3 is subjected to flotation desulfurization operation. 40 g / t of collector (butyl xanthate) is added to the grinding product 3. After a roughing operation, a roughing concentrate and a roughing tailing are obtained. The roughing concentrate is subjected to a blank selection operation to obtain a concentrated concentrate and a concentrated tailing. 10 g / t of collector (butyl xanthate) is added to the roughing tailing. After a scavenging operation, a scavenging concentrate and a scavenging tailing are obtained. The scavenging concentrate and the scavenging tailing are returned to the roughing operation. The final concentrated concentrate is the sulfur concentrate 2, and the scavenging tailing is the desulfurization tailing. The desulfurization tailing is returned to the shaking table re-selection operation.

[0111] (11) Sulfur concentrate 1 and sulfur concentrate 2 were subjected to copper, silver and sulfur flotation. After adding fruit shell activated carbon to sulfur concentrate 1 and sulfur concentrate 2 for de-doping and scrubbing for 1 hour, 800 g / t of depressant (lime) and 50 g / t of collector (sulfur nitrogen nitrile ester) were added. After a roughing operation, a roughing concentrate and a roughing tailing were obtained. 400 g / t of depressant (lime) was added to the roughing concentrate. After the first concentration, a concentrated 1 concentrate and a concentrated 1 tailing were obtained. 200 g / t of inhibitor was added to the concentrated 1 concentrate. The depressant (lime) is added to the concentrate 2, and after the second concentration, the concentrate 2 and tailings are obtained. 100g / t of depressant (lime) is added to the concentrate 2, and after the third concentration, the concentrate 3 and tailings are obtained. 10g / t of collector (sulfur nitrogen nitrile ester) is added to the roughing tailings, and after a scavenging, the scavenging concentrate and tailings are obtained; the scavenging concentrate and tailings of the concentrate 1 are returned to the roughing operation, the tailings of the concentrate 2 are returned to the first concentration operation, and the tailings of the concentrate 3 are returned to the second concentration 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 recoveries of zinc and silver were 78.28% and 10.77%, respectively.

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

[0114] Comparative Examples 1-3 and Example 1 use the same samples to carry out the test of mineral processing technology and reagents. Comparative Example 1 simplifies the process flow, directly enters the zinc-sulfur separation operation after zinc-sulfur separation and zinc-sulfur co-floatation, no longer performs copper-silver-sulfur flotation, and replaces the collector and the depressant with conventional reagents. Finally, the silver and copper grades and recovery rates in the silver-copper concentrate obtained in Comparative Example 1 are reduced, and the zinc and silver grades and recovery rates in the zinc-silver concentrate are also reduced to varying degrees. Comparative Example 2 only simplifies the process flow, directly enters the zinc-sulfur separation operation after zinc-sulfur separation and zinc-sulfur co-floatation, and no longer performs copper-silver-sulfur flotation. The zinc and silver grades and recovery rates in the zinc-silver concentrate are reduced. Comparative Example 3 has the same process as Example 1, only the collector and the depressant are replaced with conventional reagents, and the silver and copper grades and recovery rates in the silver-copper concentrate obtained are reduced to varying degrees, and the zinc and silver grades and recovery rates in the zinc-silver concentrate obtained are also reduced.

Claims

1. A method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ores, characterized in that: The following steps are involved: S1, rough grinding the raw ore, and then grinding after slurry adjustment to obtain grinding products; S2, subjecting the grinding product obtained in S1 to copper-silver flotation, wherein the copper-silver flotation process includes adding a collector for roughing, adding an inhibitor for concentrating and scavenging, and obtaining a silver-copper concentrate 1 and a silver-copper tailings; S3, subjecting the silver-copper tailings obtained in S2 to zinc-sulfur mixed flotation, wherein the zinc-sulfur mixed flotation process comprises adding an activator and a collector for roughing and concentrating, and adding a collector for scavenging to obtain zinc-sulfur mixed flotation concentrate and zinc-sulfur mixed flotation tailings; S4, classifying the zinc-sulfur mixed flotation concentrate obtained in S3 to obtain a coarse particle product and a fine particle product, and grinding the fine particle product to obtain a ground product; S5, the grinding product obtained in S4 is subjected to de-drug scrubbing and then enters the zinc-sulfur separation operation, and the zinc-sulfur separation process includes adding an inhibitor and a collector for roughing, adding an inhibitor for fine selection, and adding a collector for scavenging to obtain zinc concentrate and sulfur concentrate 1; S6, the zinc-sulfur mixed flotation tailings obtained in S3 are put into a shaking table for gravity separation to obtain a shaking table concentrate, a shaking table intermediate ore and a shaking table tailings, and the shaking table intermediate ore is ground to obtain a grinding product; S7, the grinding product obtained in S6 enters the flotation desulfurization operation, and the flotation desulfurization process includes adding a collector for roughing, concentrating and scavenging to obtain sulfur concentrate 2 and desulfurized tailings; S8. The sulfur concentrate 1 obtained from S5 and the sulfur concentrate 2 obtained from S7 are subjected to copper-silver-sulfur flotation after being scrubbed and de-doped. The copper-silver-sulfur flotation process comprises adding inhibitors and collectors for roughing, adding inhibitors for fine selection, and adding collectors for scavenging to obtain silver-copper concentrate 2 and sulfur concentrate.

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

3. The method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ore according to claim 1, characterized in that: In step S2, the collector is a mixture of thiocyanate and allylthiocarbamate isobutyl ester 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 the sodium-containing compound A is sodium sulfide or sodium hydrosulfide, and the sodium compound B is sodium carbonate or sodium sulfite.

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

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

6. The method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ore according to claim 1, characterized in that: In step S4, the mass of particles with a size smaller than 0.043 mm in the ground ore product accounts for 75-85% of the total particle mass.

7. The method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ore according to claim 1, characterized in that: In step S5, the drug removal scrubbing is as follows: adding coconut shell activated carbon or fruit shell activated carbon as a drug removal agent for drug removal scrubbing, and the scrubbing time is 0.5-1h; adding a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 as an inhibitor in the roughing stage, adding a mixture of ethylthiocarbamate, α-terpene alcohol and dithiocarbamate in a mass ratio of 2-3:1:2-3 as a collector in the roughing stage, adding a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 as an inhibitor in the fine selection stage, and adding a mixture of ethylthiocarbamate, α-terpene alcohol and dithiocarbamate in a mass ratio of 2-3:1:2-3 as a collector in the scavenging stage.

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

9. The method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ore according to claim 1, characterized in that: The collector in step S7 is sodium dihydroxymethyl propanedixanthate or isopentyl xanthate.

10. The method for recovering copper and silver from complex tin-silver-copper-zinc polymetallic ore according to claim 1, characterized in that: In step S8, the drug removal scrubbing is as follows: adding coconut shell activated carbon or fruit shell activated carbon as a drug removal agent for drug removal scrubbing, and the scrubbing time is 1.5-2h; adding a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 as an inhibitor in the rough selection stage, adding a mixture of thiocyanate and allylthiocarbamate in a mass ratio of 3-5:1 as a collector in the rough selection stage, adding a mixture of sodium silicate and calcium hydroxide in a mass ratio of 1:3-5 as an inhibitor in the fine selection stage, and adding a mixture of thiocyanate and allylthiocarbamate in a mass ratio of 3-5:1 as a collector in the scavenging stage.

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