Beneficiation method for indium and tin in bulk concentrate after recovery of ore materials

Abstract

Disclosed in the present invention is a beneficiation method for indium and tin in a bulk concentrate after recovery of ore materials, comprising the following steps: 1) carrying out ore grinding, and then carrying out bulk flotation on copper, zinc, sulfur and the like, and then carrying out copper cleaning; 2) combining cleaner tailings of a bulk and secondary scavenging tailings for indium-rich zinc-sulfur bulk flotation; 3) further carrying out indium-rich flotation on a zinc-sulfur concentrate; 4) separating the scavenging tailings by means of a centrifugal concentrator for tin enrichment; and 5) combining coarse-grained tailings, coarse-grained re-concentrated tin tailings, fine-grained tailings and fine-grained re-concentrated tin tailings, achieving efficient enrichment of indium and tin. The process flow is simple, the efficiency is greatly improved, the indium recovery rate reaches 80% or more, and the tin recovery rate reaches 85% or more.

Description

A method for beneficiating indium and tin in a mixed concentrate after ore recovery. Technical Field

[0001] This invention relates to the field of ore beneficiation technology, and in particular to a method for beneficiating indium and tin in mixed concentrate after ore material recovery. Background Technology

[0002] Indium, as a strategic rare and precious metal resource, has been widely used in fields such as computers, energy, electronics, communications, optoelectronics, medicine, health, national defense, aerospace, nuclear industry, and modern information industry. my country has the world's largest reserves of indium, but there are relatively few standalone indium deposits. Indium is mainly associated with non-ferrous metal deposits such as copper, lead, zinc, and tin. In these polymetallic sulfide deposits, indium is mainly hosted in sphalerite, forming indium-rich sphalerite, which is enriched along with zinc during the beneficiation process.

[0003] Tin is a metallic element, an inorganic compound. Common white tin is a low-melting-point metal with a silvery-white luster. In compounds, it is divalent or tetravalent and does not oxidize in air at room temperature. In nature, it mainly exists in the form of oxides (cassiterite) and various sulfides (such as staurolite).

[0004] Currently, indium is enriched through sphalerite, but the ore also contains a large amount of tin. However, due to the fine particle size of sphalerite, cassiterite and other minerals, they are difficult to liberate, resulting in low recovery efficiency. Improving the ore beneficiation recovery rate is of great significance for ensuring my country's tin and indium resource supply.

[0005] Summary of the Invention

[0006] The purpose of this invention is to provide a method for beneficiating indium and tin in mixed concentrate after ore material recovery.

[0007] The solution of the present invention is:

[0008] A method for beneficiating indium and tin in a mixed concentrate after ore recovery, comprising the following steps:

[0009] 1) Grinding: After crushing and grinding, the fineness of the mixed concentrate is 80-85% -0.074mm. Then, zinc sulfate, ethyl thiocyanate, ethyl thiocyanate and frother are added in sequence. After stirring and adjusting the slurry, a first roughing process is carried out to obtain a first roughing concentrate and a first roughing tailings. Ethyl thiocyanate and ethyl thiocyanate are added to the first roughing tailings for a first scavenging process to obtain a first scavenging concentrate and a first scavenging tailings. The first scavenging concentrate is returned to the first roughing process. Ethyl thiocyanate is added to the first scavenging tailings to adjust the slurry and a second scavenging process is carried out to obtain a second scavenging concentrate and a second scavenging tailings. The second scavenging concentrate is returned to the first scavenging process.

[0010] The roughing concentrate is classified by hydrocyclone. After classification, the sediment removed by the hydrocyclone is regrinded. The regrinded product is combined with the hydrocyclone overflow to obtain a mixture. Zinc sulfate and lime are added to the mixture for slurry preparation, and then copper concentrate is selected from the mixture. The pH of the copper concentrate slurry is 10-11, and copper concentrate and copper tailings are obtained from the mixture.

[0011] 2) Combine the copper concentrate tailings and secondary scavenging tailings, add an activator, butyl xanthate, and frother in sequence, mix and adjust the slurry, and then perform a first mixed roughing to obtain a first zinc-sulfur roughing ore and a first zinc-sulfur roughing tailings. The first zinc-sulfur roughing ore is then subjected to a first zinc-sulfur cleaning to obtain a first zinc-sulfur concentrate and a first zinc-sulfur concentrate tailings. The first zinc-sulfur concentrate tailings are returned to the mixing and adjusting slurry operation. The first zinc-sulfur concentrate is then subjected to a second zinc-sulfur cleaning to obtain a zinc-sulfur concentrate and a second zinc-sulfur concentrate tailings. The second zinc-sulfur concentrate tailings are returned to the first mixed roughing operation. Butyl xanthate and an activator are added to the first zinc-sulfur roughing tailings, and after adjusting the slurry, zinc-sulfur scavenging is performed to obtain a scavenging concentrate and scavenging tailings. The scavenging concentrate is returned to the mixing and adjusting slurry operation.

[0012] 3) The zinc-sulfur concentrate is mixed with lime to form a slurry, and then zinc is refined to obtain zinc concentrate and zinc tailings;

[0013] 4) Scavenging tailings and zinc beneficiation tailings are separated by a centrifugal concentrator to obtain centrifugal tailings and separated ore. The separated ore is classified, and the +0.045mm particle size ore is subjected to coarse-grained shaking table gravity separation to obtain coarse-grained gravity separation tin concentrate, coarse-grained middlings and coarse-grained tailings. The coarse-grained middlings are subjected to coarse-grained re-separation to obtain coarse-grained re-separation tin concentrate and coarse-grained re-separation tin tailings.

[0014] After classification, the -0.045mm particle size ore is subjected to fine-grained shaking table gravity separation to obtain fine-grained gravity separation tin concentrate, fine-grained middlings and fine-grained tailings. The fine-grained middlings are then subjected to fine-grained re-separation to obtain fine-grained re-separation tin concentrate and fine-grained re-separation tin tailings.

[0015] The coarse-grained gravity-separated tin concentrate, the coarse-grained re-separated tin concentrate, the fine-grained gravity-separated tin concentrate, and the fine-grained re-separated tin concentrate are combined to obtain tin concentrate.

[0016] 5) Combine the coarse tailings, coarse re-selected tin tailings, fine tailings, and fine re-selected tin tailings, and sequentially add sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate, and an activator. After slurry conditioning, perform tin roughing to obtain tin roughing ore and tin roughing tailings. Add sodium silicate to the tin roughing ore for primary tin cleaning to obtain primary tin concentrate and primary tin concentrate tailings. Add sodium silicate to the primary tin concentrate for secondary tin cleaning to obtain flotation tin concentrate and secondary tin concentrate tailings. Return the secondary tin concentrate tailings to the primary washing and cleaning operation. Return the primary tin concentrate tailings to the tin roughing operation. Add an activator to the tin roughing tailings for primary tin scavenging to obtain primary tin scavenged ore and primary tin scavenged tailings. Return the primary tin scavenged ore to the tin roughing operation. Add an activator to the primary tin scavenged tailings for secondary tin scavenging to obtain secondary tin scavenged ore and secondary tailings. Return the secondary tin scavenged tailings to the primary tin scavenging operation.

[0017] As a preferred technical solution, in step 1), 500g / t zinc sulfate, 100g / t ethyl thiocyanate, 70g / t ethyl nitrogen and 25g / t frother are added sequentially per ton of raw ore, and after stirring and adjusting the slurry, a roughing process is carried out.

[0018] For each ton of raw ore, 25 g / t of ethyl thiocyanate and 30 g / t of ethyl nitrogen are added to the tailings from the first roughing process for a scavenging process;

[0019] For each ton of raw ore, 30g / t of ethyl thiocyanate is added to the tailings from the first scavenging process for secondary scavenging.

[0020] As a preferred technical solution, in step 1), 700g / t zinc sulfate and 800g / t lime are added to the mixture per ton of raw ore for slurry preparation, followed by fine selection of the mixture.

[0021] As a preferred technical solution, in step 2), 800-1000 g / t of activator, 20 g / t of butyl xanthate, and 15-20 g / t of frother are added sequentially per ton of raw ore. After mixing and adjusting the slurry, a first mixing roughing is carried out. The activator includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.5.

[0022] As a preferred technical solution, in step 2), 80g / t butyl xanthate and 300g / t activator are added to the tailings of the primary zinc-sulfur roughing process per ton of raw ore, and zinc-sulfur scavenging is carried out after slurry preparation.

[0023] As a preferred technical solution, in step 4), 500g / t sulfuric acid, 200g / t alkyl phosphoric acid, 20g / t sodium silicate, 100g / t palladium nitrate, and 150-200g / t activator are added sequentially per ton of raw ore to adjust the slurry before tin roughing.

[0024] As a preferred technical solution, in step 4), based on each ton of raw ore, 50-70 g / t of activator is added to the tin roughing tailings for a first tin scavenging process to obtain a first tin scavenging ore and a first tin scavenging tailings. The first tin scavenging ore is returned to the tin roughing operation. The first tin scavenging tailings are added to 50-70 g / t of activator for a second tin scavenging process.

[0025] As a preferred technical solution, based on each ton of raw ore, 100g / t of sodium silicate is added to the tin roughing ore for primary tin refining to obtain primary tin refined ore and primary tin refined tailings. The primary tin refined ore is then added to 50g / t of sodium silicate for secondary tin refining to obtain flotation tin concentrate and secondary tin refined tailings.

[0026] As a preferred technical solution, the active agent includes 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether and octylphenol, with a dosage ratio of 20:45:25:10:2.

[0027] Advantages of this invention:

[0028] This invention targets polymetallic concentrates containing copper, zinc, sulfur, and tin. First, copper is separated by flotation, then zinc, indium, and sulfur are floated, and finally, zinc is refined to enrich indium. Tin-containing tailings are treated through multiple flotation processes to obtain tin concentrate. This method reduces the interference of impurities on tin and indium beneficiation, laying an excellent foundation for tin and indium beneficiation. Furthermore, by combining various reagents, the adverse effects of other minerals on indium and tin beneficiation are reduced, further optimizing the beneficiation environment. This achieves highly efficient enrichment of indium and tin, with a simple process flow and significantly improved efficiency, resulting in an indium recovery rate of over 80% and a tin recovery rate of over 85%.

[0029] This invention significantly improves mineral processing technical indicators, achieving higher concentrate grades than existing technologies. It fully leverages the synergistic effect between various reagents during the mineral processing process, resulting in good selectivity, strong collecting ability, stable flotation foam, and fast tin mineral flotation speed, thus achieving higher concentrate grades than the original collectors. Attached Figure Description

[0030] Figure 1 is a flowchart of the present invention. Detailed Implementation

[0031] To make the technical means, creative features, objectives and effects of this invention easier to understand, the invention will be further described below with reference to specific embodiments.

[0032] The following embodiments are only for further detailed description of the present invention, but do not constitute any limitation on the present invention; the materials used in the following embodiments, unless otherwise specified, were purchased from conventional chemical reagent companies and raw material suppliers.

[0033] Example 1:

[0034] The ore was selected from a mining area in Yunnan Province. The ore contained an average of 0.34% copper, 2.12% zinc, 11.6% sulfur, 0.76% tin, 12.3% iron, 106.2 g / t indium, and 18.7% silicon dioxide. Tin and indium minerals were the main targets for recovery.

[0035] 1) Grinding: After crushing and grinding, the mixed concentrate has a grinding fineness of -0.074mm (85%). Zinc sulfate, ethyl thiocyanate, ethyl thiocyanate, and frother are then added sequentially. After stirring and adjusting the slurry, a primary roughing process is performed to obtain a primary roughing concentrate and primary roughing tailings. The primary roughing tailings are then added to ethyl thiocyanate and ethyl thiocyanate for a primary scavenging process to obtain a primary scavenging concentrate and primary scavenging tailings. The primary scavenging concentrate is returned to the primary roughing process. The primary scavenging tailings are then added to ethyl thiocyanate for slurry adjustment and a secondary scavenging process to obtain a secondary scavenging concentrate and secondary scavenging tailings. The secondary scavenging concentrate is returned to the primary scavenging process.

[0036] The roughing concentrate is classified by hydrocyclone. After classification, the sediment removed by the hydrocyclone is regrinded. The regrinded product is combined with the hydrocyclone overflow to obtain a mixture. Zinc sulfate and lime are added to the mixture for slurry preparation, and then copper concentrate is selected from the mixture. The pH of the copper concentrate slurry is 10-11, and copper concentrate and copper tailings are obtained from the mixture.

[0037] 2) Combine the copper concentrate tailings and secondary scavenging tailings, add an activator, butyl xanthate, and frother in sequence, mix and adjust the slurry, and then perform a first mixed roughing to obtain a first zinc-sulfur roughing ore and a first zinc-sulfur roughing tailings. The first zinc-sulfur roughing ore is then subjected to a first zinc-sulfur cleaning to obtain a first zinc-sulfur concentrate and a first zinc-sulfur concentrate tailings. The first zinc-sulfur concentrate tailings are returned to the mixing and adjusting slurry operation. The first zinc-sulfur concentrate is then subjected to a second zinc-sulfur cleaning to obtain a zinc-sulfur concentrate and a second zinc-sulfur concentrate tailings. The second zinc-sulfur concentrate tailings are returned to the first mixed roughing operation. Butyl xanthate and an activator are added to the first zinc-sulfur roughing tailings, and after adjusting the slurry, zinc-sulfur scavenging is performed to obtain a scavenging concentrate and scavenging tailings. The scavenging concentrate is returned to the mixing and adjusting slurry operation.

[0038] 3) The zinc-sulfur concentrate is mixed with lime to form a slurry, and then zinc is refined to obtain zinc concentrate and zinc tailings;

[0039] 4) Scavenging tailings and zinc beneficiation tailings are separated by a centrifugal concentrator to obtain centrifugal tailings and separated ore. The separated ore is classified, and the +0.045mm particle size ore is subjected to coarse-grained shaking table gravity separation to obtain coarse-grained gravity separation tin concentrate, coarse-grained middlings and coarse-grained tailings. The coarse-grained middlings are subjected to coarse-grained re-separation to obtain coarse-grained re-separation tin concentrate and coarse-grained re-separation tin tailings.

[0040] After classification, the -0.045mm particle size ore is subjected to fine-grained shaking table gravity separation to obtain fine-grained gravity separation tin concentrate, fine-grained middlings and fine-grained tailings. The fine-grained middlings are then subjected to fine-grained re-separation to obtain fine-grained re-separation tin concentrate and fine-grained re-separation tin tailings.

[0041] The coarse-grained gravity-separated tin concentrate, the coarse-grained re-separated tin concentrate, the fine-grained gravity-separated tin concentrate, and the fine-grained re-separated tin concentrate are combined to obtain tin concentrate.

[0042] 5) Combine the coarse tailings, coarse re-selected tin tailings, fine tailings, and fine re-selected tin tailings, and sequentially add sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate, and an activator. After slurry conditioning, perform tin roughing to obtain tin roughing ore and tin roughing tailings. Add sodium silicate to the tin roughing ore for primary tin cleaning to obtain primary tin concentrate and primary tin concentrate tailings. Add sodium silicate to the primary tin concentrate for secondary tin cleaning to obtain flotation tin concentrate and secondary tin concentrate tailings. Return the secondary tin concentrate tailings to the primary washing and cleaning operation. Return the primary tin concentrate tailings to the tin roughing operation. Add an activator to the tin roughing tailings for primary tin scavenging to obtain primary tin scavenged ore and primary tin scavenged tailings. Return the primary tin scavenged ore to the tin roughing operation. Add an activator to the primary tin scavenged tailings for secondary tin scavenging to obtain secondary tin scavenged ore and secondary tailings. Return the secondary tin scavenged tailings to the primary tin scavenging operation.

[0043] In step 1), based on each ton of raw ore, 500g / t zinc sulfate, 100g / t ethyl thiocyanate, 70g / t ethyl nitrogen and 25g / t frother BK-206 are added sequentially, and after stirring and adjusting the slurry, a roughing process is carried out.

[0044] For each ton of raw ore, 25 g / t of ethyl thiocyanate and 30 g / t of ethyl nitrogen are added to the tailings from the first roughing process for a scavenging process;

[0045] For each ton of raw ore, 30g / t of ethyl thiocyanate is added to the tailings from the first scavenging process for secondary scavenging.

[0046] In step 1), based on one ton of raw ore, 700g / t of zinc sulfate and 800g / t of lime are added to the mixture for slurry preparation before the mixture is finely selected.

[0047] Therefore, for every ton of raw ore, 800g / t of enhancing activator, 20g / t of butyl xanthate, and 15g / t of frother BK-206 are added sequentially. After mixing and adjusting the slurry, a first mixing roughing is carried out. The enhancing activator includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.5.

[0048] In step 2), based on each ton of raw ore, 80g / t butyl xanthate and 300g / t activator are added to the tailings of the first zinc-sulfur roughing process, and zinc-sulfur scavenging is carried out after slurry preparation.

[0049] Add 800g / t of lime in step 3).

[0050] In step 4), based on each ton of raw ore, 500g / t sulfuric acid, 200g / t alkyl phosphoric acid, 20g / t sodium silicate, 100g / t palladium nitrate, and 150g / t activator are added sequentially to adjust the slurry before tin roughing.

[0051] As a preferred technical solution, in step 4), based on each ton of raw ore, 50g / t of activator is added to the tin roughing tailings for a first tin scavenging process to obtain a first tin scavenging ore and a first tin scavenging tailings. The first tin scavenging ore is returned to the tin roughing operation. The first tin scavenging tailings are added to 50g / t of activator for a second tin scavenging process.

[0052] Based on each ton of raw ore, 100g / t of sodium silicate is added to the tin roughing ore for primary tin refining, resulting in primary tin concentrate and primary tin tailings. 50g / t of sodium silicate is added to the primary tin concentrate for secondary tin refining, resulting in flotation tin concentrate and secondary tin tailings.

[0053] The active ingredient comprises 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether, and octylphenol, in a dosage ratio of 20:45:25:10:2.

[0054] The preparation process of oleic acid sulfated soap is as follows:

[0055] Oleic acid is used as the basic raw material. 10% to 20% of the oleic acid mass of concentrated sulfuric acid is added to it for esterification reaction for 40 to 90 minutes. The concentration of the concentrated sulfuric acid is not less than 88%. After the esterification reaction is completed, caustic soda is added to the reaction product for neutralization, and the pH value is adjusted to 7.0 to 7.5. The reaction is carried out for 1 to 1.5 hours to obtain oleic acid sulfuric acid soap.

[0056] Add pine oil, octylphenol, and nonylphenol polyoxyethylene ether to oleic acid sulfate soap according to the above ratio, stir and react at room temperature for 0.5 to 1 hour. After the reaction is complete, add 2-ethylhexanoic anhydride to the product, stir and mix at room temperature for 0.5 to 1 hour to obtain the active agent.

[0057] The final zinc concentrate contained 45.44% zinc and 908.7 g / t indium. The indium recovery rate was 81.94%, and the tin recovery rate was 85.26%.

[0058] Example 2:

[0059] The ore was selected from a mining area in Yunnan Province. The ore contained an average of 0.56% copper, 3.24% zinc, 10.5% sulfur, 0.84% ​​tin, 10.5% iron, 96.8 g / t indium, and 18.1% silicon dioxide. Tin and indium minerals were the main targets for recovery.

[0060] 1) Grinding: After crushing and grinding, the mixed concentrate has a grinding fineness of -0.074mm (85%). Then, sodium humate, zinc sulfate, ethyl thiocyanate, ethyl thiocyanate and acrylonitrile are added in sequence. After stirring and adjusting the slurry, a first roughing process is carried out to obtain a first roughing concentrate and a first roughing tailings. Ethyl thiocyanate and ethyl thiocyanate are added to the first roughing tailings for a first scavenging process to obtain a first scavenging concentrate and a first scavenging tailings. The first scavenging concentrate is returned to the first roughing process. Ethyl thiocyanate is added to the first scavenging tailings for slurry adjustment and a second scavenging process is carried out to obtain a second scavenging concentrate and a second scavenging tailings. The second scavenging concentrate is returned to the first scavenging process.

[0061] The roughing concentrate is classified by hydrocyclone. After classification, the sediment removed by the hydrocyclone is regrinded. The regrinded product is combined with the hydrocyclone overflow to obtain a mixture. Zinc sulfate and lime are added to the mixture for slurry preparation, and then copper concentrate is selected from the mixture. The pH of the copper concentrate slurry is 10-11, and copper concentrate and copper tailings are obtained from the mixture.

[0062] 2) Combine the copper concentrate tailings and secondary scavenging tailings, add an activator, butyl xanthate, and frother in sequence, mix and adjust the slurry, and then perform a first mixed roughing to obtain a first zinc-sulfur roughing ore and a first zinc-sulfur roughing tailings. The first zinc-sulfur roughing ore is then subjected to a first zinc-sulfur cleaning to obtain a first zinc-sulfur concentrate and a first zinc-sulfur concentrate tailings. The first zinc-sulfur concentrate tailings are returned to the mixing and adjusting slurry operation. The first zinc-sulfur concentrate is then subjected to a second zinc-sulfur cleaning to obtain a zinc-sulfur concentrate and a second zinc-sulfur concentrate tailings. The second zinc-sulfur concentrate tailings are returned to the first mixed roughing operation. Butyl xanthate and an activator are added to the first zinc-sulfur roughing tailings, and after adjusting the slurry, zinc-sulfur scavenging is performed to obtain a scavenging concentrate and scavenging tailings. The scavenging concentrate is returned to the mixing and adjusting slurry operation.

[0063] 3) The zinc-sulfur concentrate is mixed with lime to form a slurry, and then zinc is refined to obtain zinc concentrate and zinc tailings;

[0064] 4) Scavenging tailings and zinc beneficiation tailings are separated by a centrifugal concentrator to obtain centrifugal tailings and separated ore. The separated ore is classified, and the +0.045mm particle size ore is subjected to coarse-grained shaking table gravity separation to obtain coarse-grained gravity separation tin concentrate, coarse-grained middlings and coarse-grained tailings. The coarse-grained middlings are subjected to coarse-grained re-separation to obtain coarse-grained re-separation tin concentrate and coarse-grained re-separation tin tailings.

[0065] After classification, the -0.045mm particle size ore is subjected to fine-grained shaking table gravity separation to obtain fine-grained gravity separation tin concentrate, fine-grained middlings and fine-grained tailings. The fine-grained middlings are then subjected to fine-grained re-separation to obtain fine-grained re-separation tin concentrate and fine-grained re-separation tin tailings.

[0066] The coarse-grained gravity-separated tin concentrate, the coarse-grained re-separated tin concentrate, the fine-grained gravity-separated tin concentrate, and the fine-grained re-separated tin concentrate are combined to obtain tin concentrate.

[0067] 5) Combine the coarse tailings, coarse re-selected tin tailings, fine tailings, and fine re-selected tin tailings, and sequentially add sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate, and an activator. After slurry conditioning, perform tin roughing to obtain tin roughing ore and tin roughing tailings. Add sodium silicate to the tin roughing ore for primary tin cleaning to obtain primary tin concentrate and primary tin concentrate tailings. Add sodium silicate to the primary tin concentrate for secondary tin cleaning to obtain flotation tin concentrate and secondary tin concentrate tailings. Return the secondary tin concentrate tailings to the primary washing and cleaning operation. Return the primary tin concentrate tailings to the tin roughing operation. Add an activator to the tin roughing tailings for primary tin scavenging to obtain primary tin scavenged ore and primary tin scavenged tailings. Return the primary tin scavenged ore to the tin roughing operation. Add an activator to the primary tin scavenged tailings for secondary tin scavenging to obtain secondary tin scavenged ore and secondary tailings. Return the secondary tin scavenged tailings to the primary tin scavenging operation.

[0068] In step 1), based on each ton of raw ore, 500g / t zinc sulfate, 100g / t ethyl thiocyanate, 70g / t ethyl nitrogen and 25g / t frother BK-206 are added sequentially, and after stirring and adjusting the slurry, a roughing process is carried out.

[0069] For each ton of raw ore, 25 g / t of ethyl thiocyanate and 30 g / t of ethyl nitrogen are added to the tailings from the first roughing process for a scavenging process;

[0070] For each ton of raw ore, 30g / t of ethyl thiocyanate is added to the tailings from the first scavenging process for secondary scavenging.

[0071] In step 1), based on one ton of raw ore, 700g / t of zinc sulfate and 800g / t of lime are added to the mixture for slurry preparation before the mixture is finely selected.

[0072] Therefore, for every ton of raw ore, 900g / t of enhancing activator, 20g / t of butyl xanthate, and 20g / t of frother BK-206 are added sequentially. After mixing and adjusting the slurry, a first mixing roughing is carried out. The enhancing activator includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.5.

[0073] In step 2), based on each ton of raw ore, 80g / t butyl xanthate and 300g / t activator are added to the tailings of the first zinc-sulfur roughing process, and zinc-sulfur scavenging is carried out after slurry preparation.

[0074] In step 3), 700 g / t of lime is added.

[0075] In step 4), based on each ton of raw ore, 500g / t sulfuric acid, 200g / t alkyl phosphoric acid, 20g / t sodium silicate, 100g / t palladium nitrate, and 180g / t activator are added sequentially to adjust the slurry before tin roughing.

[0076] In step 4), based on each ton of raw ore, 60g / t of activator is added to the tin roughing tailings for a first tin scavenging process to obtain a first tin scavenged ore and a first tin scavenged tailings. The first tin scavenged ore is returned to the tin roughing operation. The first tin scavenged tailings are added to 60g / t of activator for a second tin scavenging process.

[0077] Based on each ton of raw ore, 100g / t of sodium silicate is added to the tin roughing ore for primary tin refining, resulting in primary tin concentrate and primary tin tailings. 50g / t of sodium silicate is added to the primary tin concentrate for secondary tin refining, resulting in flotation tin concentrate and secondary tin tailings.

[0078] The active ingredient comprises 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether, and octylphenol, in a dosage ratio of 20:45:25:10:2.

[0079] The preparation process of oleic acid sulfated soap is as follows:

[0080] Oleic acid is used as the basic raw material. 10% to 20% of the oleic acid mass of concentrated sulfuric acid is added to it for esterification reaction for 40 to 90 minutes. The concentration of the concentrated sulfuric acid is not less than 88%. After the esterification reaction is completed, caustic soda is added to the reaction product for neutralization, and the pH value is adjusted to 7.0 to 7.5. The reaction is carried out for 1 to 1.5 hours to obtain oleic acid sulfuric acid soap.

[0081] Add pine oil, octylphenol, and nonylphenol polyoxyethylene ether to oleic acid sulfate soap according to the above ratio, stir and react at room temperature for 0.5 to 1 hour. After the reaction is complete, add 2-ethylhexanoic anhydride to the product, stir and mix at room temperature for 0.5 to 1 hour to obtain the active agent.

[0082] The recovery rate for indium was 82.43%, and the recovery rate for tin was 85.48%.

[0083] Example 3:

[0084] The ore was selected from a mining area in Yunnan Province. The ore contained an average of 0.92% copper, 1.85% zinc, 10.3% sulfur, 0.84% ​​tin, 14.4% iron, 110.5 g / t indium, and 17.5% silicon dioxide. Tin and indium minerals were the main targets for recovery.

[0085] 1) Grinding: After crushing and grinding, the mixed concentrate has a grinding fineness of -0.074mm (80%). Then, sodium humate, zinc sulfate, ethyl thiocyanate, ethyl thiocyanate and acrylonitrile are added in sequence. After stirring and adjusting the slurry, a first roughing process is carried out to obtain a first roughing concentrate and a first roughing tailings. Ethyl thiocyanate and ethyl thiocyanate are added to the first roughing tailings for a first scavenging process to obtain a first scavenging concentrate and a first scavenging tailings. The first scavenging concentrate is returned to the first roughing process. Ethyl thiocyanate is added to the first scavenging tailings to adjust the slurry and a second scavenging process is carried out to obtain a second scavenging concentrate and a second scavenging tailings. The second scavenging concentrate is returned to the first scavenging process.

[0086] The roughing concentrate is classified by hydrocyclone. After classification, the sediment removed by the hydrocyclone is regrinded. The regrinded product is combined with the hydrocyclone overflow to obtain a mixture. Zinc sulfate and lime are added to the mixture for slurry preparation, and then copper concentrate is selected from the mixture. The pH of the copper concentrate slurry is 10-11, and copper concentrate and copper tailings are obtained from the mixture.

[0087] 2) Combine the copper concentrate tailings and secondary scavenging tailings, add an activator, butyl xanthate, and frother in sequence, mix and adjust the slurry, and then perform a first mixed roughing to obtain a first zinc-sulfur roughing ore and a first zinc-sulfur roughing tailings. The first zinc-sulfur roughing ore is then subjected to a first zinc-sulfur cleaning to obtain a first zinc-sulfur concentrate and a first zinc-sulfur concentrate tailings. The first zinc-sulfur concentrate tailings are returned to the mixing and adjusting slurry operation. The first zinc-sulfur concentrate is then subjected to a second zinc-sulfur cleaning to obtain a zinc-sulfur concentrate and a second zinc-sulfur concentrate tailings. The second zinc-sulfur concentrate tailings are returned to the first mixed roughing operation. Butyl xanthate and an activator are added to the first zinc-sulfur roughing tailings, and after adjusting the slurry, zinc-sulfur scavenging is performed to obtain a scavenging concentrate and scavenging tailings. The scavenging concentrate is returned to the mixing and adjusting slurry operation.

[0088] 3) The zinc-sulfur concentrate is mixed with lime to form a slurry, and then zinc is refined to obtain zinc concentrate and zinc tailings;

[0089] 4) Scavenging tailings and zinc beneficiation tailings are separated by a centrifugal concentrator to obtain centrifugal tailings and separated ore. The separated ore is classified, and the +0.045mm particle size ore is subjected to coarse-grained shaking table gravity separation to obtain coarse-grained gravity separation tin concentrate, coarse-grained middlings and coarse-grained tailings. The coarse-grained middlings are subjected to coarse-grained re-separation to obtain coarse-grained re-separation tin concentrate and coarse-grained re-separation tin tailings.

[0090] After classification, the -0.045mm particle size ore is subjected to fine-grained shaking table gravity separation to obtain fine-grained gravity separation tin concentrate, fine-grained middlings and fine-grained tailings. The fine-grained middlings are then subjected to fine-grained re-separation to obtain fine-grained re-separation tin concentrate and fine-grained re-separation tin tailings.

[0091] The coarse-grained gravity-separated tin concentrate, the coarse-grained re-separated tin concentrate, the fine-grained gravity-separated tin concentrate, and the fine-grained re-separated tin concentrate are combined to obtain tin concentrate.

[0092] 5) Combine the coarse tailings, coarse re-selected tin tailings, fine tailings, and fine re-selected tin tailings, and sequentially add sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate, and an activator. After slurry conditioning, perform tin roughing to obtain tin roughing ore and tin roughing tailings. Add sodium silicate to the tin roughing ore for primary tin cleaning to obtain primary tin concentrate and primary tin concentrate tailings. Add sodium silicate to the primary tin concentrate for secondary tin cleaning to obtain flotation tin concentrate and secondary tin concentrate tailings. Return the secondary tin concentrate tailings to the primary washing and cleaning operation. Return the primary tin concentrate tailings to the tin roughing operation. Add an activator to the tin roughing tailings for primary tin scavenging to obtain primary tin scavenged ore and primary tin scavenged tailings. Return the primary tin scavenged ore to the tin roughing operation. Add an activator to the primary tin scavenged tailings for secondary tin scavenging to obtain secondary tin scavenged ore and secondary tailings. Return the secondary tin scavenged tailings to the primary tin scavenging operation.

[0093] In step 1), based on each ton of raw ore, 500g / t zinc sulfate, 100g / t ethyl thiocyanate, 70g / t ethyl nitrogen and 25g / t frother BK-206 are added sequentially, and after stirring and adjusting the slurry, a roughing process is carried out.

[0094] For each ton of raw ore, 25 g / t of ethyl thiocyanate and 30 g / t of ethyl nitrogen are added to the tailings from the first roughing process for a scavenging process;

[0095] For each ton of raw ore, 30g / t of ethyl thiocyanate is added to the tailings from the first scavenging process for secondary scavenging.

[0096] In step 1), based on one ton of raw ore, 700g / t of zinc sulfate and 800g / t of lime are added to the mixture for slurry preparation before the mixture is finely selected.

[0097] Therefore, for every ton of raw ore, 1000g / t of enhancing activator, 20g / t of butyl xanthate, and 20g / t of frother BK-206 are added sequentially. After mixing and adjusting the slurry, a first mixing roughing is carried out. The enhancing activator includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.5.

[0098] In step 2), based on each ton of raw ore, 80g / t butyl xanthate and 300g / t activator are added to the tailings of the first zinc-sulfur roughing process, and zinc-sulfur scavenging is carried out after slurry preparation.

[0099] In step 3), add 600g / t of lime.

[0100] In step 4), 500g / t sulfuric acid, 200g / t alkyl phosphoric acid, 20g / t sodium silicate, 100g / t palladium nitrate, and 200g / t activator are added sequentially per ton of raw ore to adjust the slurry before tin roughing.

[0101] In step 4), based on each ton of raw ore, 70g / t of activator is added to the tin roughing tailings for a first tin scavenging process to obtain a first tin scavenged ore and a first tin scavenged tailings. The first tin scavenged ore is returned to the tin roughing operation. The first tin scavenged tailings are added to 70g / t of activator for a second tin scavenging process.

[0102] Based on each ton of raw ore, 100g / t of sodium silicate is added to the tin roughing ore for primary tin refining, resulting in primary tin concentrate and primary tin tailings. 50g / t of sodium silicate is added to the primary tin concentrate for secondary tin refining, resulting in flotation tin concentrate and secondary tin tailings.

[0103] The active ingredient comprises 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether, and octylphenol, in a dosage ratio of 20:45:25:10:2.

[0104] The preparation process of oleic acid sulfated soap is as follows:

[0105] Oleic acid is used as the basic raw material. 10% to 20% of the oleic acid mass of concentrated sulfuric acid is added to it for esterification reaction for 40 to 90 minutes. The concentration of the concentrated sulfuric acid is not less than 88%. After the esterification reaction is completed, caustic soda is added to the reaction product for neutralization, and the pH value is adjusted to 7.0 to 7.5. The reaction is carried out for 1 to 1.5 hours to obtain oleic acid sulfuric acid soap.

[0106] Add pine oil, octylphenol, and nonylphenol polyoxyethylene ether to oleic acid sulfate soap according to the above ratio, stir and react at room temperature for 0.5 to 1 hour. After the reaction is complete, add 2-ethylhexanoic anhydride to the product, stir and mix at room temperature for 0.5 to 1 hour to obtain the active agent.

[0107] The recovery rates for indium and tin were 83.05% and 85.53%, respectively. This demonstrates that the invention not only improves ore beneficiation efficiency but also efficiently recovers resources such as zinc and indium.

[0108] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for beneficiating indium and tin in a mixed concentrate after ore material recovery, characterized in that, Includes the following steps: 1) Grinding: After crushing and grinding, the fineness of the mixed concentrate is 80-85% -0.074mm. Then, zinc sulfate, ethyl thiocyanate, ethyl thiocyanate and frother are added in sequence. After stirring and adjusting the slurry, a first roughing process is carried out to obtain a first roughing concentrate and a first roughing tailings. Ethyl thiocyanate and ethyl thiocyanate are added to the first roughing tailings for a first scavenging process to obtain a first scavenging concentrate and a first scavenging tailings. The first scavenging concentrate is returned to the first roughing process. Ethyl thiocyanate is added to the first scavenging tailings to adjust the slurry and a second scavenging process is carried out to obtain a second scavenging concentrate and a second scavenging tailings. The second scavenging concentrate is returned to the first scavenging process. The roughing concentrate is classified by hydrocyclone. After classification, the sediment removed by the hydrocyclone is regrinded. The regrinded product is combined with the hydrocyclone overflow to obtain a mixture. Zinc sulfate and lime are added to the mixture for slurry preparation, and then copper concentrate is selected from the mixture. The pH of the copper concentrate slurry is 10-11, and copper concentrate and copper tailings are obtained from the mixture. 2) Combine the copper concentrate tailings and secondary scavenging tailings, add an activator, butyl xanthate, and frother in sequence, mix and adjust the slurry, and then perform a first mixed roughing to obtain a first zinc-sulfur roughing ore and a first zinc-sulfur roughing tailings. The first zinc-sulfur roughing ore is then subjected to a first zinc-sulfur cleaning to obtain a first zinc-sulfur concentrate and a first zinc-sulfur concentrate tailings. The first zinc-sulfur concentrate tailings are returned to the mixing and adjusting slurry operation. The first zinc-sulfur concentrate is then subjected to a second zinc-sulfur cleaning to obtain a zinc-sulfur concentrate and a second zinc-sulfur concentrate tailings. The second zinc-sulfur concentrate tailings are returned to the first mixed roughing operation. Butyl xanthate and an activator are added to the first zinc-sulfur roughing tailings, and after adjusting the slurry, zinc-sulfur scavenging is performed to obtain a scavenging concentrate and scavenging tailings. The scavenging concentrate is returned to the mixing and adjusting slurry operation. 3) The zinc-sulfur concentrate is mixed with lime to form a slurry, and then zinc is refined to obtain zinc concentrate and zinc tailings; 4) Scavenging tailings and zinc beneficiation tailings are separated by a centrifugal concentrator to obtain centrifugal tailings and separated ore. The separated ore is classified, and the +0.045mm particle size ore is subjected to coarse-grained shaking table gravity separation to obtain coarse-grained gravity separation tin concentrate, coarse-grained middlings and coarse-grained tailings. The coarse-grained middlings are subjected to coarse-grained re-separation to obtain coarse-grained re-separation tin concentrate and coarse-grained re-separation tin tailings. After classification, the -0.045mm particle size ore is subjected to fine-grained shaking table gravity separation to obtain fine-grained gravity separation tin concentrate, fine-grained middlings and fine-grained tailings. The fine-grained middlings are then subjected to fine-grained re-separation to obtain fine-grained re-separation tin concentrate and fine-grained re-separation tin tailings. The coarse-grained gravity-separated tin concentrate, the coarse-grained re-separated tin concentrate, the fine-grained gravity-separated tin concentrate, and the fine-grained re-separated tin concentrate are combined to obtain tin concentrate. 5) Combine the coarse tailings, coarse re-selected tin tailings, fine tailings, and fine re-selected tin tailings, and sequentially add sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate, and an activator. After slurry preparation, perform tin roughing to obtain tin roughing ore and tin roughing tailings. Add sodium silicate to the tin roughing ore for primary tin cleaning to obtain primary tin concentrate and primary tin concentrate tailings. Add sodium silicate to the primary tin concentrate for secondary tin cleaning to obtain flotation tin concentrate and secondary tin concentrate tailings. The secondary tin concentrate tailings are returned to the primary washing and cleaning operation; the primary tin concentrate tailings are returned to the tin roughing operation. Add an activator to the tin roughing tailings for primary tin scavenging to obtain primary tin scavenged ore and primary tin scavenged tailings. The primary tin scavenged ore is returned to the tin roughing operation. Add an activator to the primary tin scavenged tailings for secondary tin scavenging to obtain secondary tin scavenged ore and secondary tailings. The tailings are returned to the tin scavenging operation.

2. The method for beneficiating indium and tin in a mixed concentrate after ore recovery as described in claim 1, characterized in that: In step 1), based on each ton of raw ore, 500g / t zinc sulfate, 100g / t ethyl thiocyanate, 70g / t ethyl nitrogen and 25g / t frother are added sequentially, and after stirring and adjusting the slurry, a roughing process is carried out. For each ton of raw ore, 25 g / t of ethyl thiocyanate and 30 g / t of ethyl nitrogen are added to the tailings from the first roughing process for a scavenging process; For each ton of raw ore, 30g / t of ethyl thiocyanate is added to the tailings from the first scavenging process for secondary scavenging.

3. The method for beneficiating indium and tin in a mixed concentrate after ore recovery as described in claim 2, characterized in that: In step 1), based on one ton of raw ore, 700g / t of zinc sulfate and 800g / t of lime are added to the mixture for slurry preparation before the mixture is finely selected.

4. The method for beneficiating indium and tin in a mixed concentrate after ore recovery as described in claim 1, characterized in that: In step 2), 800-1000 g / t of activator, 20 g / t of butyl xanthate, and 15-20 g / t of frother are added sequentially per ton of raw ore. After mixing and adjusting the slurry, a first mixing roughing is carried out. The activator includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.

5.

5. The method for beneficiating indium and tin in a mixed concentrate after ore recovery as described in claim 1, characterized in that: In step 2), 80 g / t butyl xanthate and 300 g / t activator are added to the tailings of the first zinc-sulfur roughing process per ton of raw ore, and zinc-sulfur scavenging is carried out after slurry preparation.

6. The method for beneficiating indium and tin in a mixed concentrate after ore recovery as described in claim 1, characterized in that: In step 4), based on one ton of raw ore, 500g / t sulfuric acid, 200g / t alkyl phosphoric acid, 20g / t sodium silicate, 100g / t palladium nitrate, and 150-200g / t activator are added sequentially to adjust the slurry before tin roughing.

7. The method for beneficiating indium and tin in a mixed concentrate after ore material recovery as described in claim 6, characterized in that: In step 4), based on each ton of raw ore, 50-70 g / t of activator is added to the tin roughing tailings for a first tin scavenging process to obtain a first tin scavenged ore and a first tin scavenged tailings. The first tin scavenged ore is returned to the tin roughing operation. The first tin scavenged tailings are added to 50-70 g / t of activator for a second tin scavenging process.

8. The method for beneficiating indium and tin in a mixed concentrate after ore recovery as described in claim 1, characterized in that: Based on each ton of raw ore, 100g / t of sodium silicate is added to the tin roughing ore for primary tin refining, resulting in primary tin concentrate and primary tin tailings. 50g / t of sodium silicate is added to the primary tin concentrate for secondary tin refining, resulting in flotation tin concentrate and secondary tin tailings.

9. A method for beneficiating indium and tin in a mixed concentrate after ore recovery, as described in claim 6 or 7, characterized in that: The active ingredient comprises 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether, and octylphenol, in a dosage ratio of 20:45:25:10:2.

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