Beneficiation method for shallow low-temperature hydrothermal copper-lead-zinc polymetallic ore

Abstract

The invention discloses a beneficiation method for shallow low-temperature hydrothermal copper-lead-zinc polymetallic ore, which comprises the following steps: S1, ore to be treated is ground until the ore with the fineness of-0.074 mm accounts for 60-70%, and a material a is obtained; s2, the material a is subjected to copper-lead mixed separation operation, and copper-lead mixed concentrate and copper-lead tailings are obtained; s3, carrying out copper-lead separation operation on the copper-lead bulk concentrate to obtain copper concentrate and lead concentrate; s4, zinc separation operation is conducted on the copper-lead tailings, and zinc concentrate and zinc separation tailings are obtained; s5, sulfur separation operation is conducted on the zinc separation tailings, and sulfur concentrate and sulfur separation tailings are obtained; and S6, the sulfur separation tailings are subjected to aftertreatment operation, and the white carbon black is obtained. The flotation process of copper and lead mixed separation, copper and lead separation, zinc re-separation of copper and lead tailings and sulfur re-separation of zinc separation tailings is combined with the heating alkaline leaching and sulfuric acid precipitation process, and copper concentrate, lead concentrate, zinc concentrate, sulfur concentrate and white carbon black are obtained respectively.

Description

Technical Field

[0001] This invention relates to the field of ore separation technology, and in particular to a beneficiation method for shallow low-temperature hydrothermal copper-lead-zinc polymetallic ores. Background Technology

[0002] Copper, lead, and zinc ores are crucial non-ferrous metal mineral resources. my country is a major producer, consumer, and trader of copper, lead, and zinc globally. Years of intensive mining have depleted my country's high-quality mineral resources, leading to a gradual depletion of ore grades. Therefore, the comprehensive utilization of copper, lead, and zinc resources has become a key factor influencing my country's entire copper, lead, and zinc industry. Currently, many processes in copper, lead, and zinc mining focus on recovering lead and zinc metals, often neglecting other associated metals or non-metals in the ore. With continuous technological advancements, other metals and non-metals in copper, lead, and zinc ores can be processed into higher-value products, creating economic benefits, reducing tailings dam volume, and fixing heavy metal ions in tailings to prevent secondary pollution, aligning with sustainable development strategies.

[0003] Therefore, existing technologies still need improvement and development. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the purpose of this invention is to provide a beneficiation method for shallow low-temperature hydrothermal copper-lead-zinc polymetallic ores, which aims to solve the problem that the prior art neglects other associated metals or non-metals in the ore.

[0005] The technical solution of the present invention is as follows: In a first aspect, the present invention provides a method for beneficiating shallow, low-temperature hydrothermal copper-lead-zinc polymetallic ores, the beneficiation method comprising the following steps: S1. Grind the ore to be processed until the fineness of the ore is -0.074mm and the proportion is 60~70%, to obtain material a; S2. Perform copper-lead mixed flotation on material a: zinc sulfate, 25# black reagent, and isopropyl xanthate are added to material a in sequence, and copper-lead rough concentrate b and copper-lead rough tailings c are obtained by flotation; copper-lead rough concentrate b is subjected to 2-3 blank cleaning processes to obtain copper-lead mixed concentrate d; zinc sulfate and 25# black reagent are added to copper-lead rough tailings c in sequence, and copper-lead tailings e are obtained by 2-3 scavenging processes. S3. Copper-lead separation operation on copper-lead mixed concentrate d: Add activated carbon to copper-lead mixed concentrate d for de-processing, then add sodium sulfite, sodium humate and ethyl thiocyanate, and obtain copper rough concentrate f and copper rough tailings g by flotation; add sodium sulfite to copper rough concentrate f, and obtain copper concentrate by 2-3 blank cleaning; add sodium sulfite and ethyl thiocyanate to copper rough tailings g in sequence, and obtain lead concentrate by 2-3 scavenging. S4. Zinc beneficiation of copper-lead tailings e: Add lime to copper-lead roughing tailings c to adjust the pH to 10-12, then add copper sulfate, butyl xanthate and No. 2 oil. After flotation, zinc rough concentrate h and zinc roughing tailings i are obtained; add lime to zinc rough concentrate h and after 2-3 cleaning processes, zinc concentrate is obtained; add lime, copper sulfate and butyl xanthate to zinc roughing tailings i and after 2-3 scavenging processes, zinc beneficiation tailings j are obtained. S5. Sulfurization of zinc tailings j: Add sulfuric acid to zinc tailings j to adjust the pH to 7-8, then add copper sulfate, butyl xanthate and No. 2 oil. After flotation of pyrite, obtain pyrite rough concentrate k and pyrite rough tailings m. After 2-3 blank cleanings of pyrite rough concentrate k, obtain sulfur concentrate. Add copper sulfate and butyl xanthate to pyrite rough tailings m, and after 2-3 scavengings, obtain sulfur tailings n. S6. Post-processing of sulfur tailings n: Add water and sodium hydroxide to sulfur tailings n and heat to leach. After solid-liquid separation, leachate p and leachate slag q are obtained. Add sodium sulfate electrolyte to leachate p, then add sulfuric acid solution and react. After reaction, the solid is obtained by aging and solid-liquid separation. The solid is washed and dried to obtain silica.

[0006] Optionally, in step S2, the step of sequentially adding zinc sulfate, 25# black reagent, and isopropyl xanthate to material a, and obtaining copper-lead rough concentrate b and copper-lead rough tailings c by flotation, specifically includes: adding zinc sulfate to material a, stirring for 2-4 minutes, then adding 25# black reagent, stirring for 1-2 minutes, then adding isopropyl xanthate, stirring for 1-2 minutes, and then performing flotation to obtain copper-lead rough concentrate b and copper-lead rough tailings c.

[0007] Preferably, the amount of zinc sulfate added is 500~1000g / t, the amount of 25# black powder added is 50~100g / t, and the amount of isopropyl xanthate added is 10~30g / t.

[0008] Optionally, in step S2, zinc sulfate and 25# black powder are added sequentially to the copper-lead roughing tailings c, and copper-lead tailings e are obtained after 2-3 scavenging processes. The amount of 25# black powder added is 10-30 g / t.

[0009] Optionally, in step S3, the step of adding activated carbon to the copper-lead mixed concentrate d for de-removal, then adding sodium sulfite, sodium humate and ethyl thiocyanate, and obtaining copper rough concentrate f and copper rough tailings g by flotation specifically includes: adding activated carbon to the copper-lead mixed concentrate d and stirring for 5-10 minutes for de-removal, then adding sodium sulfite and sodium humate and stirring for 2-4 minutes, then adding ethyl thiocyanate and stirring for 1-2 minutes, and finally flotation to obtain copper rough concentrate f and copper rough tailings g.

[0010] Preferably, the amount of sodium sulfite added is 500~1000g / t, the amount of sodium humate added is 100~300g / t, and the amount of ethyl thiocyanate added is 20~40g / t.

[0011] Optionally, in step S3, when sodium sulfite is added to the copper crude concentrate f and the copper concentrate is obtained after 2-3 blank cleaning processes, the amount of sodium sulfite added is 100~300g / t.

[0012] Optionally, in step S3, sodium sulfite and ethyl thiocyanate are added sequentially to the copper roughing tailings g, and the lead concentrate is obtained after 2-3 scavenging processes. The amount of sodium sulfite added is 200-400 g / t, and the amount of ethyl thiocyanate added is 10-20 g / t.

[0013] Optionally, in step S4, lime is added to the copper-lead roughing tailings c to adjust the pH to 10-12, and then copper sulfate, butyl xanthate and No. 2 oil are added. After flotation, zinc rough concentrate h and zinc roughing tailings i are obtained. The amount of lime added is 3000-6000 g / t.

[0014] Optionally, in step S5, when sulfuric acid is added to the zinc tailings j to adjust the pH to 7-8, the amount of sulfuric acid added is 500-800 g / t.

[0015] Beneficial effects: This invention provides a beneficiation method for shallow, low-temperature hydrothermal copper-lead-zinc polymetallic ores. Compared with existing technologies, the advantages of this invention are: 1. This invention combines a flotation process of copper-lead mixed beneficiation-copper-lead separation-copper-lead tailings re-zinc beneficiation-zinc tailings re-sulfur beneficiation with a process of heated alkaline leaching and sulfuric acid precipitation to obtain five products: copper concentrate, lead concentrate, zinc concentrate, sulfur concentrate, and silica.

[0016] 2. For copper and lead ores, this invention employs a method of first co-flotation of copper and lead, followed by separation of copper and lead. Firstly, both chalcopyrite and galena are naturally floatable minerals with good floatability; secondly, the floatability of chalcopyrite and galena is very similar. Therefore, this invention, by first co-flotting copper and lead minerals, then co-flotting the tailings, and finally separating zinc minerals, both accommodates the floatability of the minerals and reduces reagent usage, simplifying the process flow. Attached Figure Description

[0017] Figure 1 A flowchart illustrating the beneficiation method for shallow low-temperature hydrothermal copper-lead-zinc polymetallic ores provided in an embodiment of the present invention. Detailed Implementation

[0018] This invention provides a beneficiation method for shallow, low-temperature hydrothermal copper-lead-zinc polymetallic ores. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below.

[0019] In shallow, low-temperature hydrothermal copper-lead-zinc polymetallic ores, copper ore typically accounts for a low proportion, which increases the difficulty of beneficiation and recovery. At the same time, since copper and lead minerals in shallow, low-temperature hydrothermal copper-lead-zinc polymetallic ores have similar floatability, traditional reagents have difficulty selectively collecting copper and lead minerals, making it difficult to achieve efficient separation. Therefore, copper-lead separation has always been one of the challenges in the mineral beneficiation industry.

[0020] Based on this, embodiments of the present invention provide a beneficiation method for shallow low-temperature hydrothermal copper-lead-zinc polymetallic ores, the beneficiation method comprising the following steps: S1. Grind the ore to be processed until the fineness of the ore is -0.074mm and the proportion is 60~70%, to obtain material a; S2. Perform copper-lead mixed flotation on material a: zinc sulfate, 25# black reagent, and isopropyl xanthate are added to material a in sequence, and copper-lead rough concentrate b and copper-lead rough tailings c are obtained by flotation; copper-lead rough concentrate b is subjected to 2-3 blank cleaning processes to obtain copper-lead mixed concentrate d; zinc sulfate and 25# black reagent are added to copper-lead rough tailings c in sequence, and copper-lead tailings e are obtained by 2-3 scavenging processes. S3. Copper-lead separation operation on copper-lead mixed concentrate d: Add activated carbon to copper-lead mixed concentrate d for de-processing, then add sodium sulfite, sodium humate and ethyl thiocyanate, and obtain copper rough concentrate f and copper rough tailings g by flotation; add sodium sulfite to copper rough concentrate f, and obtain copper concentrate by 2-3 blank cleaning; add sodium sulfite and ethyl thiocyanate to copper rough tailings g in sequence, and obtain lead concentrate by 2-3 scavenging. S4. Zinc beneficiation of copper-lead tailings e: Add lime to copper-lead roughing tailings c to adjust the pH to 10-12, then add copper sulfate, butyl xanthate and No. 2 oil. After flotation, zinc rough concentrate h and zinc roughing tailings i are obtained; add lime to zinc rough concentrate h and after 2-3 cleaning processes, zinc concentrate is obtained; add lime, copper sulfate and butyl xanthate to zinc roughing tailings i and after 2-3 scavenging processes, zinc beneficiation tailings j are obtained. S5. Sulfurization of zinc tailings j: Add sulfuric acid to zinc tailings j to adjust the pH to 7-8, then add copper sulfate, butyl xanthate and No. 2 oil. After flotation of pyrite, obtain pyrite rough concentrate k and pyrite rough tailings m. After 2-3 blank cleanings of pyrite rough concentrate k, obtain sulfur concentrate. Add copper sulfate and butyl xanthate to pyrite rough tailings m, and after 2-3 scavengings, obtain sulfur tailings n. S6. Post-processing of sulfur tailings n: Add water and sodium hydroxide to sulfur tailings n and heat to leach. After solid-liquid separation, leachate p and leachate slag q are obtained. Add sodium sulfate electrolyte to leachate p, then add sulfuric acid solution and react. After reaction, the solid is obtained by aging and solid-liquid separation. The solid is washed and dried to obtain silica.

[0021] like Figure 1 As shown, the method provided in this embodiment of the invention combines a flotation process of copper-lead mixed beneficiation-copper-lead separation-copper-lead tailings re-zinc beneficiation-zinc tailings re-sulfur beneficiation with a process of heated alkaline leaching and sulfuric acid precipitation, to obtain five products: copper concentrate, lead concentrate, zinc concentrate, sulfur concentrate, and silica. This not only improves the value of the products but also reduces tailings emissions, pointing the way for the comprehensive utilization of shallow low-temperature hydrothermal copper-lead-zinc polymetallic ores.

[0022] For copper and lead ores, this invention employs a method of first co-floting copper and lead, followed by separation of copper and lead. In shallow, low-temperature hydrothermal copper-lead-zinc polymetallic ores, copper is dominated by chalcopyrite, and lead by galena. Firstly, both chalcopyrite and galena are naturally floatable minerals with good floatability; secondly, the floatability of chalcopyrite and galena is very similar. Therefore, this invention, by first co-flotting copper and lead minerals, then co-flotting the tailings, and finally separating zinc minerals, both accommodates the floatability of the minerals and reduces reagent usage, simplifying the process.

[0023] In some embodiments, step S2, which involves sequentially adding zinc sulfate, 25# black reagent, and isopropyl xanthate to material a, and then flotation to obtain copper-lead rough concentrate b and copper-lead rough tailings c, specifically includes: adding zinc sulfate to material a, stirring for 2-4 minutes, then adding 25# black reagent, stirring for 1-2 minutes, then adding isopropyl xanthate, stirring for 1-2 minutes, and then flotation to obtain copper-lead rough concentrate b and copper-lead rough tailings c.

[0024] Since No. 25 black powder exhibits the best selectivity for galena, and isopropyl xanthate shows the best selectivity for chalcopyrite, in this embodiment, No. 25 black powder is added first, stirred for 1 minute, followed by the addition of isopropyl xanthate and stirring for another 1 minute. In this embodiment, the combined use of No. 25 black powder and isopropyl xanthate achieves a synergistic and complementary effect, effectively capturing copper and lead ore from shallow, low-temperature hydrothermal copper-lead-zinc polymetallic ores.

[0025] In this embodiment, during the copper-lead mixed flotation operation, after adding 25# black powder and stirring for 1 minute, isopropyl xanthate is added at a rate of 10-30 g / t, and the mixture is stirred for 1 minute for flotation. Under the premise of not affecting the lead recovery rate and grade, the copper recovery rate can be increased by 10-20%.

[0026] Preferably, in step S2, the amount of zinc sulfate added is 500~1000g / t, the amount of 25# black powder added is 50~100g / t, and the amount of isopropyl xanthate added is 10~30g / t.

[0027] Preferably, in step S2, zinc sulfate and 25# black powder are added sequentially to the copper-lead roughing tailings c, and after 2-3 scavenging processes, copper-lead tailings e are obtained. The amount of 25# black powder added is 10-30 g / t.

[0028] In this embodiment, step S2 specifically includes the following steps: 1) Add zinc sulfate to material a, stir for 2-4 minutes, then add No. 25 black powder, stir for 1-2 minutes, then add isopropyl xanthate, stir for 1-2 minutes, and then perform flotation to obtain copper-lead rough concentrate b and copper-lead rough tailings c. 2) The copper-lead rough concentrate b is subjected to blank cleaning 2-3 times to obtain copper-lead mixed concentrate d; the tailings are returned to the previous operation in sequence; 3) Add zinc sulfate to the copper-lead roughing tailings c, stir for 2-4 minutes, then add 25# black reagent, stir for 1-2 minutes, and perform 2-3 scavenging to obtain copper-lead tailings e; the concentrate is returned to the previous operation in sequence.

[0029] In some embodiments, step S3, which involves adding activated carbon to the copper-lead mixed concentrate d for descaling, then adding sodium sulfite, sodium humate, and ethyl thiocyanate, and finally flotation to obtain copper rough concentrate f and copper roughing tailings g, specifically includes: adding activated carbon to the copper-lead mixed concentrate d and stirring for 5-10 minutes for descaling, then adding sodium sulfite and sodium humate and stirring for 2-4 minutes, then adding ethyl thiocyanate and stirring for 1-2 minutes, and finally flotation to obtain copper rough concentrate f and copper roughing tailings g.

[0030] Preferably, the amount of sodium sulfite added is 500~1000g / t, the amount of sodium humate added is 100~300g / t, and the amount of ethyl thiocyanate added is 20~40g / t.

[0031] In this embodiment, flotation is performed by first adding 500-1000 g / t of sodium sulfite and stirring for 3 minutes, then adding 100-300 g / t of sodium humate and stirring for 3 minutes, and finally adding 20-40 g / t of ethyl thiocyanate and stirring for 1 minute. Specifically, sodium sulfite inhibits galena and eliminates the influence of inevitable ions; sodium humate strengthens the inhibition of galena and also inhibits pyrite; and ethyl thiocyanate acts as a collector for chalcopyrite, thus collecting chalcopyrite.

[0032] Preferably, in step S3, when sodium sulfite is added to the copper crude concentrate f and the copper concentrate is obtained after 2-3 blank cleaning processes, the amount of sodium sulfite added is 100-300 g / t.

[0033] Preferably, in step S3, sodium sulfite and ethyl thiocyanate are added sequentially to the copper roughing tailings g, and the lead concentrate is obtained after 2-3 scavenging processes. The amount of sodium sulfite added is 200-400 g / t, and the amount of ethyl thiocyanate added is 10-20 g / t.

[0034] In this embodiment, step S3 specifically includes the following steps: 1) Add activated carbon to material d and stir for 5-10 minutes to remove the reagent. Then add sodium sulfite and sodium humate and stir for 2-4 minutes. Then add ethyl thiocyanate and stir for 1-2 minutes. Then perform flotation to obtain copper rough concentrate f and copper rough tailings g. 2) Add sodium sulfite to the copper crude concentrate f, stir for 2-4 minutes, and perform 2-3 cleaning processes to obtain copper concentrate; return the tailings to the previous operation in sequence; 3) Add sodium sulfite to the copper roughing tailings g, stir for 2-4 minutes, then add ethyl thiocyanate, stir for 1-2 minutes, and perform 2-3 scavenging processes to obtain lead concentrate; return the concentrate to the previous operation in sequence.

[0035] In some embodiments, in step S4, lime is added to copper-lead roughing tailings c to adjust the pH to 10-12, and then copper sulfate, butyl xanthate and No. 2 oil are added. After flotation, zinc rough concentrate h and zinc roughing tailings i are obtained. The amount of lime added is 3000-6000 g / t.

[0036] In this embodiment, lime is used to adjust the pH of the slurry to the range of 10-11, while suppressing pyrite.

[0037] In this embodiment, step S4 specifically includes the following steps: 1) Add lime to lead tailings c, control the pH at 10~12 and stir for 2~4 minutes, then add copper sulfate and stir for 2~4 minutes, then add butyl xanthate and No. 2 oil, stir for 1~2 minutes and then carry out flotation to obtain zinc rough concentrate h and zinc rough tailings i. 2) Add lime to the zinc crude concentrate h, stir for 2-4 minutes, and perform 3-4 cleaning processes to obtain zinc concentrate; return the tailings to the previous operation. 3) Add lime to zinc roughing tailings i and stir for 2-4 minutes. Then add copper sulfate and stir for 2-4 minutes. Then add butyl xanthate and stir for 1-2 minutes. Perform 3-4 scavenging cycles to obtain the tailings, which are zinc tailings j. The concentrate is returned to the previous operation.

[0038] In some embodiments, in step S5, when sulfuric acid is added to the zinc tailings j to adjust the pH to 7-8, the amount of sulfuric acid added is 500-800 g / t.

[0039] In this embodiment, sulfuric acid is used to adjust the pH of the slurry to 7-8 and also to activate the pyrite.

[0040] In this embodiment, step S5 specifically includes the following steps: 1) Add sulfuric acid to zinc tailings j, control the pH at 7-8, then add copper sulfate, stir for 2-4 minutes, then add butyl xanthate and No. 2 oil, stir for 1-2 minutes, and then float pyrite to obtain pyrite rough concentrate k and pyrite rough tailings m. 2) The concentrate obtained by passing the pyrite rough concentrate k through two blank cleaning processes is called pyrite concentrate; the tailings are returned to the previous operation in sequence; 3) Add copper sulfate to the roughing tailings m of pyrite, stir for 2-4 minutes, then add butyl xanthate, stir for 1-2 minutes, and perform two scavenging processes. The tailings obtained are the pyrite tailings n; the concentrate is returned to the previous operation.

[0041] In some embodiments, step S6 specifically includes the following steps: 1) After adding water and sodium hydroxide to the sulfur tailings n, the mixture is heated and leached in a reactor. After solid-liquid separation, leachate p and leaching residue q are obtained. 2) Add sodium sulfate electrolyte to the leachate p, and add 8-12% sulfuric acid solution dropwise in a constant temperature water bath at 70-90℃ for 1-2 hours. Control the pH at the end of the reaction to be 6.5-7.5. After the reaction is completed, age the product at a constant temperature of 70-90℃ for 1.5-2.5 hours. Separate the solid and liquid, wash the obtained solid repeatedly with water, and dry it to obtain hydrated silica (white carbon black).

[0042] In some embodiments, the beneficiation method for shallow low-temperature hydrothermal copper-lead-zinc polymetallic ores is specifically operated as follows: S1. First, take 3000g of shallow low-temperature hydrothermal ore (the amount of ore depends on the copper grade of the ore, the purpose is to facilitate copper flotation) and grind it to -0.074mm, accounting for 60~70%, to achieve the liberation of minerals. Mix the ore with water and place it in an 8L flotation cell with a liquid-solid ratio of 2:1 to prepare for flotation. S2. First, mix and float copper sulfide minerals and lead sulfide minerals. Before flotation, add 500~1000g / t of zinc sulfate and stir for 3 minutes. Then add 50~100g / t of No. 25 black powder and 10~30g / t of isopropyl xanthate. Stir for 1 minute and start flotation. The flotation foam is the copper-lead mixed rough concentrate. Perform blank cleaning 2~3 times on the copper-lead mixed rough concentrate to obtain a copper-lead mixed concentrate containing more than 60% lead and more than 1% copper. S3. For copper-lead mixed concentrate, copper and lead separation is carried out by first adding 500-1000 g / t of activated carbon and stirring for 8 minutes for de-reagent removal. Then, 500-1000 g / t of sodium sulfite and 100-300 g / t of sodium humate are added and stirred for 3 minutes. Then, 20-40 g / t of ethyl thiocyanate is added and stirred for 1 minute before flotation to obtain copper rough concentrate and copper roughing tailings. After adding a small amount of sodium sulfite to the copper rough concentrate, two cleaning processes are carried out to obtain copper concentrate with a copper content of more than 20%. After adding a small amount of sodium sulfite and ethyl thiocyanate to the copper roughing tailings, two scavenging processes are carried out to obtain lead concentrate with a lead content of more than 60%.

[0043] S4. For lead tailings, further float zinc sulfide minerals. Before flotation, add 3000-6000 g / t of lime, control the pH at 10-12, and stir for 3 minutes. Then add 100-200 g / t of copper sulfate and stir for 3 minutes. Next, add 80-140 g / t of butyl xanthate and 20-40 g / t of No. 2 oil, and stir for 1 minute before starting flotation. The flotation froth is the zinc rough concentrate. The zinc rough concentrate is then refined 2-3 times, adding 300-600 g / t of lime during each refinement to obtain a zinc concentrate containing over 50% zinc. For the zinc roughing tailings, add a small amount of lime, copper sulfate, and butyl xanthate, and scaveng 2-3 times to obtain the zinc-refined tailings. S5. For zinc tailings, further flotation of iron sulfide minerals is performed. Before flotation, 500-800 g / t of sulfuric acid is added to adjust the slurry, controlling the pH at 7-8. Then, 50-100 g / t of copper sulfate is added, and the mixture is stirred for 3 minutes. 50-100 g / t of butyl xanthate and 20-40 g / t of No. 2 oil are added, and flotation begins after stirring for 1 minute. The flotation froth is the iron sulfide rough concentrate. The iron sulfide rough concentrate is then subjected to 2-3 blank cleaning cycles to obtain a sulfur concentrate containing over 45% sulfur. For the iron sulfide roughing tailings, a small amount of copper sulfate and butyl xanthate are added, and the mixture is scavenged 2-3 times to obtain the sulfur-refined tailings. S6. The flotation tailings, water, and sodium hydroxide are placed in a reactor for heated leaching at 220°C for 120 min. The alkali-to-residue mass ratio is 2:1, and the liquid-to-solid ratio is 5:1. After cooling to room temperature and separating the solid and liquid, leaching residue and leachate are obtained. 100 ml of leachate is placed in a beaker and placed in a constant temperature water bath. A certain amount of electrolyte sodium sulfate is added, and a prepared sulfuric acid solution is added dropwise at a certain stirring rate. The pH at the reaction endpoint is controlled to be 7, and the reaction time is 1-2 h. After the reaction is completed, the mixture is aged at a constant temperature for 2 h. After aging, the solid and liquid are separated. The solid is repeatedly washed with water and finally dried in an oven at 100°C to obtain hydrated silica, i.e., white carbon black.

[0044] The present invention will be further described below through specific embodiments.

[0045] Example 1 Take 3000g of shallow low-temperature hydrothermal copper-lead-zinc polymetallic ore (raw ore with copper grade 0.15%, lead grade 2.30%, zinc grade 3.78%, sulfur grade 7.68%, iron grade 11.31%, silica grade 50.57%, copper mainly exists in the form of chalcopyrite, lead mainly exists in the form of galena, zinc mainly exists in the form of sphalerite, iron mainly exists in the form of pyrite, and gangue minerals are mainly silicate minerals such as quartz). Grind the ore to -0.074mm with 65% of the particles. Mix the ore with water in an 8L flotation cell with a liquid-to-solid ratio of approximately 2:1. First, mix and float chalcopyrite and galena. Before flotation, add 1000g / t of zinc sulfate, stir for 3 minutes, and then add 25g / t of zinc sulfate. #Add 50g / t of black reagent and 20g / t of isopropyl xanthate (isopropyl xanthate helps enhance the recovery of copper minerals), stir for 1 minute, and then begin flotation. The flotation froth is the copper-lead mixed rough concentrate. Place the copper-lead mixed rough concentrate in a 1.5L flotation cell and perform blank cleaning 2-3 times to obtain a copper-lead mixed concentrate containing 2.47% copper and 63.16% lead. Mix the copper-lead mixed concentrate with water and place it in a 0.5L flotation cell for copper-lead separation. First, add 800g / t of activated carbon and stir for 10 minutes to ensure that the reagents on the surface of the copper-lead mixed concentrate are fully absorbed. After separation, 1000 g / t of sodium sulfite and 100 g / t of sodium humate are added and stirred for 3 minutes to suppress galena. 20 g / t of ethyl thiocyanate is added to collect chalcopyrite, and after stirring for 1 minute, flotation begins. The flotation froth is then cleaned 2-3 times, with a small amount of sodium sulfite added during the cleansing process. This yields a copper concentrate containing 22.49% copper, with a copper recovery rate of 74%. The roughing tailings are then scavenged 2-3 times with a small amount of sodium sulfite and ethyl thiocyanate. The scavenged tailings are a lead concentrate containing 66.51% lead, with a lead recovery rate of 93.08%. The copper-lead mixed tailings are then floated for sphalerite. Before flotation, 4000 g / t of lime is added to suppress pyrite, the pH is controlled at around 11, and the mixture is stirred for 3 minutes. 150 g / t of copper sulfate is added to activate the sphalerite, and after stirring for 3 minutes, 100 g / t of butyl xanthate and 2... # Add 30g / t of oil, stir for 1 minute, and then begin flotation. The flotation foam is the zinc rough concentrate. Place the zinc rough concentrate in a 1.5L flotation cell for three refining processes (500g / t of lime added for refinement 1, 300g / t of lime added for refinement 2, and no lime added for refinement 3). This yields a zinc concentrate containing 48.37% zinc, with a zinc recovery rate of 90.14%. The zinc roughing tailings undergo three scavenging processes, with a small amount of copper sulfate and butyl xanthate added during scavenging. The scavenged tailings are then the zinc tailings. The zinc tailings are then used for pyrite flotation. Before flotation, the pulp is adjusted. Due to the large amount of lime added during zinc refining, 700g / t of sulfuric acid is added to adjust the pulp pH to approximately 7. 60g / t of copper sulfate is added to activate the pyrite, and the mixture is stirred for 3 minutes. 80g / t of butyl xanthate and 2... #30g / t of oil is stirred for 1 minute before flotation begins. The flotation foam is the sulfur rough concentrate. The sulfur rough concentrate is placed in a 1.5L flotation cell for two blank cleaning cycles to obtain a sulfur concentrate with a sulfur content of 46.71% and a sulfur recovery rate of 85%. The sulfur roughing tailings are scavenged twice, with a small amount of copper sulfate and butyl xanthate added during scavenging. The scavenged tailings are the sulfur tailings. After dehydration, sulfur tailings were leached in a reactor with water and sodium hydroxide at 220°C for 120 minutes. The alkali-to-residue ratio was 2:1, and the liquid-to-solid ratio was 5:1. After cooling to room temperature and solid-liquid separation, leaching residue and leachate were obtained. 100 ml of the leachate was placed in a beaker and then placed in a constant-temperature water bath at 80°C. 3% sodium sulfate electrolyte was added, and 10% sulfuric acid solution was added dropwise with a certain stirring rate, controlling the pH at the final reaction point to be 7. The reaction time was 1-2 hours. After the reaction, the mixture was aged at a constant temperature for 2 hours. After aging, the solid and liquid were separated. The solid was repeatedly washed with water and finally dried in an oven at 100°C to obtain hydrated silica, i.e., white carbon black. The specific surface area of ​​white carbon black is 191.37 m². 2 / g, this product meets the highest category A requirements in the national standard GB / T10722.

[0046] Example 2 Take 3000g of shallow low-temperature hydrothermal copper-lead-zinc polymetallic ore (raw ore with copper grade 0.27%, lead grade 3.82%, zinc grade 5.17%, sulfur grade 9.45%, iron grade 15.03%, silica grade 45.22%, copper mainly exists in the form of chalcopyrite, lead mainly exists in the form of galena, zinc mainly exists in the form of sphalerite, iron mainly exists in the form of pyrite, and gangue minerals are mainly silicate minerals such as quartz). Grind the ore to -0.074mm (60%). Mix the ore with water in an 8L flotation cell with a liquid-to-solid ratio of approximately 2:1. First, mix and float chalcopyrite and galena. Before flotation, add 1000g / t of zinc sulfate, stir for 3 minutes, and then add 25g / t of zinc sulfate. #Add 70g / t of black reagent and 30g / t of isopropyl xanthate, stir for 1 minute, and then begin flotation. The flotation froth is the copper-lead mixed rough concentrate. Place the copper-lead mixed rough concentrate in a 1.5L flotation cell and perform blank cleaning 2-3 times to obtain a copper-lead mixed concentrate containing 3.71% copper and 65.47% lead. Mix the copper-lead mixed concentrate with water and place it in a 0.5L flotation cell for copper-lead separation. First, add 1000g / t of activated carbon and stir for 10 minutes to fully remove the reagents from the surface of the copper-lead mixed concentrate. Then add tungsten... Sodium sulfate (1000 g / t) and sodium humate (100 g / t) are stirred for 3 minutes to suppress galena. Ethyl thiocyanate (30 g / t) is added to collect chalcopyrite. After stirring for 1 minute, flotation begins. The froth obtained from flotation is cleaned 2-3 times, with a small amount of sodium sulfite added during the cleansing process. This yields a copper concentrate containing 24.18% copper, with a copper recovery rate of 81%. The roughing tailings are scavenged 2-3 times with a small amount of sodium sulfite and ethyl thiocyanate. The scavenged tailings are then a lead concentrate containing 70.13% lead, with a lead recovery rate of 93.74%. The copper-lead mixed tailings are then used for sphalerite flotation. Before flotation, lime (5000 g / t) is added to suppress pyrite, and the pH is controlled at around 11. After stirring for 3 minutes, copper sulfate (120 g / t) is added to activate the sphalerite. After stirring for 3 minutes, butyl xanthate (100 g / t) and 2... # Add 30g / t of oil, stir for 1 minute, and then begin flotation. The flotation foam is the zinc rough concentrate. Place the zinc rough concentrate in a 1.5L flotation cell for three refining processes (500g / t of lime added for refinement 1, 300g / t of lime added for refinement 2, and no lime added for refinement 3). This yields a zinc concentrate containing 52.41% zinc, with a zinc recovery rate of 92.36%. The zinc roughing tailings are then subjected to three scavenging processes, with a small amount of copper sulfate and butyl xanthate added during scavenging. The scavenged tailings are the zinc tailings. Next, pyrite is floated from the zinc tailings. First, 800g / t of sulfuric acid is added to adjust the pulp pH to approximately 7. Then, 80g / t of copper sulfate is added to activate the pyrite, and the mixture is stirred for 3 minutes. Finally, 100g / t of butyl xanthate and 2... #30g / t of oil is stirred for 1 minute before flotation begins. The flotation foam is the sulfur rough concentrate. The sulfur rough concentrate is placed in a 1.5L flotation cell for two blank cleaning cycles to obtain a sulfur concentrate with a sulfur content of 45.82% and a sulfur recovery rate of 90%. The sulfur roughing tailings are scavenged twice, with a small amount of copper sulfate and butyl xanthate added during scavenging. The scavenged tailings are the sulfur tailings. After dehydration, sulfur tailings were leached in a reactor with water and sodium hydroxide at 220°C for 120 minutes. The leaching ratio of alkali to residue was 2:1, and the liquid-to-solid ratio was 5:1. After cooling to room temperature and solid-liquid separation, leaching residue and leachate were obtained. 100 ml of the leachate was placed in a beaker and then placed in a constant-temperature water bath at 80°C. 3% sodium sulfate electrolyte was added, and 10% sulfuric acid solution was added dropwise with a certain stirring rate, controlling the pH at the final reaction point to be 7. The reaction time was 1-2 hours. After the reaction, the mixture was aged at a constant temperature for 2 hours. After aging, the solid and liquid were separated. The solid was repeatedly washed with water and finally dried in an oven at 100°C to obtain hydrated silica, i.e., white carbon black. The specific surface area of ​​white carbon black is 189.55 m². 2 / g, this product meets the highest category A requirements in the national standard GB / T10722.

[0047] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A beneficiation method for shallow, low-temperature hydrothermal copper-lead-zinc polymetallic ores, characterized in that, The mineral processing method includes the following steps: S1. Grind the ore to be processed until the fineness of the ore is -0.074mm and the proportion is 60~70%, to obtain material a; S2. Perform copper-lead mixed flotation on material a: zinc sulfate, 25# black reagent, and isopropyl xanthate are added to material a in sequence, and copper-lead rough concentrate b and copper-lead rough tailings c are obtained by flotation; copper-lead rough concentrate b is subjected to 2-3 blank cleaning processes to obtain copper-lead mixed concentrate d; zinc sulfate and 25# black reagent are added to copper-lead rough tailings c in sequence, and copper-lead tailings e are obtained by 2-3 scavenging processes. S3. Copper-lead separation operation on copper-lead mixed concentrate d: Add activated carbon to copper-lead mixed concentrate d for de-processing, then add sodium sulfite, sodium humate and ethyl thiocyanate, and obtain copper rough concentrate f and copper rough tailings g by flotation; add sodium sulfite to copper rough concentrate f, and obtain copper concentrate by 2-3 blank cleaning; add sodium sulfite and ethyl thiocyanate to copper rough tailings g in sequence, and obtain lead concentrate by 2-3 scavenging. S4. Zinc beneficiation of copper-lead tailings e: Add lime to copper-lead roughing tailings c to adjust the pH to 10-12, then add copper sulfate, butyl xanthate and No. 2 oil. After flotation, zinc rough concentrate h and zinc roughing tailings i are obtained; add lime to zinc rough concentrate h and after 2-3 cleaning processes, zinc concentrate is obtained; add lime, copper sulfate and butyl xanthate to zinc roughing tailings i and after 2-3 scavenging processes, zinc beneficiation tailings j are obtained. S5. Sulfurization of zinc tailings j: Add sulfuric acid to zinc tailings j to adjust the pH to 7-8, then add copper sulfate, butyl xanthate and No. 2 oil. After flotation of pyrite, obtain pyrite rough concentrate k and pyrite rough tailings m. After 2-3 blank cleanings of pyrite rough concentrate k, obtain sulfur concentrate. Add copper sulfate and butyl xanthate to pyrite rough tailings m, and after 2-3 scavengings, obtain sulfur tailings n. S6. Post-processing of sulfur tailings n: Add water and sodium hydroxide to sulfur tailings n and heat to leach. After solid-liquid separation, leachate p and leachate slag q are obtained. Add sodium sulfate electrolyte to leachate p, then add sulfuric acid solution and react. After reaction, the solid is obtained by aging and solid-liquid separation. The solid is washed and dried to obtain silica.

2. The mineral processing method according to claim 1, characterized in that, In step S2, the step of sequentially adding zinc sulfate, 25# black reagent, and isopropyl xanthate to material a, and obtaining copper-lead rough concentrate b and copper-lead rough tailings c by flotation specifically includes: adding zinc sulfate to material a, stirring for 2-4 minutes, then adding 25# black reagent, stirring for 1-2 minutes, then adding isopropyl xanthate, stirring for 1-2 minutes, and then performing flotation to obtain copper-lead rough concentrate b and copper-lead rough tailings c.

3. The mineral processing method according to claim 2, characterized in that, The amount of zinc sulfate added is 500~1000g / t, the amount of No. 25 black powder added is 50~100g / t, and the amount of isopropyl xanthate added is 10~30g / t.

4. The method according to claim 1, characterized in that, In step S2, zinc sulfate and No. 25 black powder are added sequentially to the copper-lead roughing tailings c. After 2-3 scavenging processes, copper-lead tailings e are obtained. The amount of No. 25 black powder added is 10-30 g / t.

5. The method according to claim 1, characterized in that, In step S3, the step of adding activated carbon to the copper-lead mixed concentrate d for de-removal, then adding sodium sulfite, sodium humate and ethyl thiocyanate, and then flotation to obtain copper rough concentrate f and copper roughing tailings g specifically includes: adding activated carbon to the copper-lead mixed concentrate d and stirring for 5-10 minutes for de-removal, then adding sodium sulfite and sodium humate and stirring for 2-4 minutes, then adding ethyl thiocyanate and stirring for 1-2 minutes, and then flotation to obtain copper rough concentrate f and copper roughing tailings g.

6. The method according to claim 5, characterized in that, The amount of sodium sulfite added is 500~1000g / t, the amount of sodium humate added is 100~300g / t, and the amount of ethyl thiocyanate added is 20~40g / t.

7. The method according to claim 1, characterized in that, In step S3, sodium sulfite is added to the copper crude concentrate f, and the copper concentrate is obtained after 2-3 blank cleaning processes. The amount of sodium sulfite added is 100-300 g / t.

8. The method according to claim 1, characterized in that, In step S3, sodium sulfite and ethyl thiocyanate are added sequentially to the copper roughing tailings g, and the lead concentrate is obtained after 2-3 scavenging processes. The amount of sodium sulfite added is 200-400 g / t, and the amount of ethyl thiocyanate added is 10-20 g / t.

9. The method according to claim 1, characterized in that, In step S4, lime is added to the copper-lead roughing tailings c to adjust the pH to 10-12, and then copper sulfate, butyl xanthate and No. 2 oil are added. After flotation, zinc rough concentrate h and zinc roughing tailings i are obtained. The amount of lime added is 3000-6000 g / t.

10. The method according to claim 1, characterized in that, In step S5, sulfuric acid is added to the zinc tailings j to adjust the pH to 7-8, and the amount of sulfuric acid added is 500-800 g / t.

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