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

Abstract

The invention discloses a beneficiation method for indium and tin in bulk concentrate after ore material recovery. The beneficiation method comprises the following steps that (1) after ore grinding, bulk flotation of copper, zinc, sulfur and the like is conducted, and then copper concentration is conducted; the method comprises the following steps: (1) cleaning tailings and secondary scavenging tailings, (2) combining the mixture cleaning tailings and the secondary scavenging tailings, and carrying out indium-rich zinc-sulfur bulk flotation, (3) carrying out further indium-rich flotation on zinc-sulfur concentrates, and (4) separating the scavenging tailings through a centrifugal separator to enrich tin; and (4) the coarse grain tailings, the coarse grain recleaning tin tailings, the fine grain tailings and the fine grain recleaning tin tailings are combined, efficient enrichment of indium and tin is achieved, the technological process is simple, the efficiency is greatly improved, the indium recovery rate reaches 80% or above, and the tin recovery rate reaches 85% or above.

Description

Technical Field

[0001] The invention relates to the technical field of ore dressing, and in particular to a method for dressing indium tin in mixed concentrate after ore material recovery. Background Art

[0002] As a strategic rare and precious metal resource, indium has been widely used in the fields of computers, energy, electronics, communications, optoelectronics, medicine, health, national defense and military, aerospace, nuclear industry and modern information industry. my country's indium resource reserves rank first in the world, but there are few independent 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 found in marmatite, forming indium-rich marmatite, which is enriched with zinc during the beneficiation process.

[0003] Tin is a metallic element, an inorganic substance. In its ordinary form, white tin is a low-melting-point metal with a silvery-white luster. It is divalent or tetravalent in compounds and will not be oxidized by air at room temperature. In nature, it mainly exists in the form of dioxide (cassiterite) and various sulfides (such as cassiterite).

[0004] Currently, indium is enriched through sphalerite, but its ore also contains a large amount of tin. However, since sphalerite, cassiterite and other minerals are embedded in fine particles and difficult to dissociate, the recovery efficiency is low. How to improve the mineral processing recovery rate is of great significance to ensuring the supply of tin and indium resources in my country. Summary of the invention

[0005] The object of the present invention is to provide a method for beneficiating indium tin in mixed concentrate after ore material recovery.

[0006] The scheme of the present invention is:

[0007] A method for beneficiating indium and tin in mixed concentrate after ore material recovery comprises the following steps:

[0008] 1) Grinding: after the mixed concentrate is crushed and ground, the grinding fineness is -0.074mm, accounting for 80-85%. Then, zinc sulfate, ethylthiocarbamate, ethylthio nitrogen and a frother are added in sequence, stirred and slurried, a roughing is performed to obtain a roughing concentrate and a roughing tailing. The roughing tailing is added with ethylthiocarbamate and ethylthio nitrogen for a scavenging to obtain a scavenging concentrate and a scavenging tailing. The scavenging concentrate is returned to the roughing operation. The scavenging tailing is added with ethylthiocarbamate for slurrying, and a secondary scavenging is performed to obtain a secondary scavenging concentrate and a secondary scavenging tailing. The secondary scavenging concentrate is returned to the primary scavenging operation;

[0009] The primary roughing concentrate is subjected to cyclone classification, and after classification, the sedimentary ore removed by the cyclone is regrinded, and the regrinding product is combined with the cyclone overflow to obtain a mixture, and zinc sulfate and lime are added to the mixture to adjust the slurry and then the mixture is copper-selected, and the pH of the copper-selected slurry of the mixture is 10-11, and the copper-selected concentrate and the copper-selected tailings of the mixture are obtained;

[0010] 2) The copper concentrate tailings and the secondary scavenging tailings of the mixture are combined, and an enhancing active agent, butyl xanthate and a frother are added in sequence. After mixing and slurrying, a mixed roughing is carried out to obtain a primary zinc-sulfur roughing ore and a primary zinc-sulfur roughing tailing. The primary zinc-sulfur roughing ore is subjected to a primary zinc-sulfur concentration to obtain a primary zinc-sulfur concentrated ore and a primary zinc-sulfur concentrated tailing, and the primary zinc-sulfur concentrated tailing is returned to the mixed slurrying operation; the primary zinc-sulfur concentrated ore is subjected to a secondary zinc-sulfur concentration to obtain a zinc-sulfur concentrate and a secondary zinc-sulfur concentrated tailing, and the secondary zinc-sulfur concentrated tailing is returned to the primary mixed roughing operation; butyl xanthate and an enhancing active agent are added to the primary zinc-sulfur roughing tailing, and zinc-sulfur scavenging is carried out after slurrying to obtain a scavenging concentrate and a scavenging tailing, and the scavenging concentrate is returned to the mixed slurrying operation;

[0011] 3) adding lime to the zinc-sulfur concentrate to prepare a slurry, and then performing zinc concentration to obtain zinc concentrated concentrate and zinc concentrated tailings;

[0012] 4) The scavenging tailings and the zinc concentrate tailings are separated by a centrifugal concentrator to obtain centrifuge tailings and separated ore, the separated ore is classified, and the classified +0.045 mm particle size ore is subjected to coarse-grained shaking table gravity selection to obtain coarse-grained gravity-selected tin concentrate, coarse-grained middlings and coarse-grained tailings, and the coarse-grained middlings are subjected to coarse-grained reselection to obtain coarse-grained reselected tin concentrate and coarse-grained reselected tin tailings;

[0013] After classification, the -0.045 mm particle size ore is subjected to fine-grained shaking table gravity selection to obtain fine-grained gravity-selected tin concentrate, fine-grained intermediate ore and fine-grained tailings, and the fine-grained intermediate ore is subjected to fine-grained reselection to obtain fine-grained reselected tin concentrate and fine-grained reselected tin tailings;

[0014] Combining the coarse-grained tin concentrate with the coarse-grained tin concentrate with the re-selected tin concentrate, the fine-grained tin concentrate with the fine-grained tin concentrate to obtain a tin concentrate;

[0015] 5) combining the coarse tailings, coarse re-selected tin tailings, fine tailings and fine re-selected tin tailings, adding sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate and an activator in sequence, and carrying out tin rough selection after slurry mixing to obtain tin rough selection and tin rough selection tailings, adding sodium silicate to the tin rough selection to carry out primary tin selection to obtain primary tin selection ore and primary tin selection tailings, adding sodium silicate to the primary tin selection ore to carry out secondary tin selection to obtain flotation tin concentrate and secondary tin selection tailings, and the secondary tin selection tailings are returned to the primary washing and selection operation; the primary tin selection tailings are returned to the tin rough selection operation; adding an activator to the tin rough selection tailings to carry out a tin scavenging selection to obtain a primary tin scavenging selection and a primary tin scavenging selection tailings, and the primary tin scavenging selection tailings are returned to the tin rough selection operation; adding an activator to the primary tin scavenging selection tailings to carry out secondary tin scavenging selection to obtain secondary tin scavenging selection and secondary tailings, and the secondary tin scavenging selection tailings are returned to the primary tin scavenging selection operation.

[0016] As a preferred technical solution, in the step 1), 500 g / t zinc sulfate, 100 g / t ethylthiocarbamate, 70 g / t ethylthiocyanate and 25 g / t foaming agent are added in sequence per ton of raw ore, and a roughing is performed after stirring and slurrying;

[0017] Calculated per ton of raw ore, 25g / t ethylthiocarbamate and 30g / t ethylthiocyanate are added to the roughing tailings for a scavenging;

[0018] Based on each ton of raw ore, 30g / t ethionamide is added to the tailings of the first scavenging process to prepare the slurry for the second scavenging process.

[0019] As a preferred technical solution, in the above 1), 700 g / t zinc sulfate and 800 g / t lime are added to the mixture for slurry preparation per ton of raw ore, and then the mixture is beneficiated.

[0020] As a preferred technical solution, in the above 2), 800-1000 g / t of enhancing active agent, 20 g / t of butyl xanthate and 15-20 g / t of foaming agent are added in sequence per ton of raw ore, and after mixing and slurrying, a mixed roughing is carried out, and the mass ratio of the enhancing active agent including copper sulfate and ammonium bicarbonate is 2:1.5.

[0021] As a preferred technical solution, in the step 2), 80 g / t butyl xanthate and 300 g / t enhancing activator are added to the primary zinc-sulfur roughing tailings per ton of raw ore, and zinc-sulfur scavenging is performed after slurry adjustment.

[0022] As a preferred technical solution, in the step 4), 500 g / t sulfuric acid, 200 g / t alkyl phosphoric acid, 20 g / t sodium silicate, 100 g / t palladium nitrate and 150-200 g / t activator are sequentially added per ton of raw ore to prepare slurry before rough tin selection.

[0023] As a preferred technical solution, in the step 4), per ton of raw ore, 50-70 g / t of initiator is added to the tin roughing tailings for a tin scavenging operation to obtain a primary tin scavenging operation and a primary tin scavenging tailings, and the primary tin scavenging operation is returned to the tin roughing operation; and 50-70 g / t of initiator is added to the primary tin scavenging tailings for a secondary tin scavenging operation.

[0024] As a preferred technical solution, per ton of raw ore, 100 g / t sodium silicate is added to the tin rough beneficiation to carry out primary tin beneficiation to obtain primary tin beneficiation ore and primary tin beneficiation tailings, and 50 g / t sodium silicate is added to the primary tin beneficiation ore to carry out secondary tin beneficiation to obtain flotation tin concentrate and secondary tin beneficiation tailings.

[0025] As a preferred technical solution, the activator includes 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether and octylphenol, and the dosage ratio thereof is 20:45:25:10:2.

[0026] Advantages of the present invention:

[0027] The present invention is aimed at polymetallic concentrates containing copper, zinc, sulfur, tin, etc., firstly flots copper to separate it, then floats zinc, indium, and sulfur, and then concentrates zinc so that indium can be enriched through zinc, and for tin-containing tailings, multiple flotations are performed to obtain tin concentrate. This method reduces the interference of impurities on the beneficiation of tin and indium, lays an excellent foundation for the beneficiation of tin and indium, and reduces the adverse effects of other types of minerals on the beneficiation of indium and tin by matching various reagents, further optimizing the beneficiation environment of indium and tin. The efficient enrichment of indium and tin is achieved, the process flow is simple, and the efficiency is greatly improved, so that the recovery rate of indium reaches more than 80%, and the recovery rate of tin reaches more than 85%.

[0028] The invention obviously improves the mineral processing technical indicators, can obtain a higher concentrate grade than the prior art, fully exerts the synergistic effect between various reagents in the mineral processing process, has good selectivity, strong collecting ability, stable flotation foam, and fast tin mineral floating speed, and can obtain a higher concentrate grade than the original collector. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 It is a process framework diagram of the present invention. DETAILED DESCRIPTION

[0030] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments.

[0031] The following examples are only used to further illustrate the present invention in detail, but do not constitute any limitation to the present invention; the materials used in the following examples, unless otherwise specified, were purchased from conventional chemical reagent companies and raw material suppliers.

[0032] Embodiment 1:

[0033] The ore is selected from a mining area in Yunnan. The average ore content is 0.34% copper, 2.12% zinc, 11.6% sulfur, 0.76% tin, 12.3% iron, 106.2g / t indium, and 18.7% silicon dioxide. Tin minerals and indium minerals are the main objects of recovery.

[0034] 1) Grinding: after the mixed concentrate is crushed and ground, the grinding fineness is -0.074mm, accounting for 85%. Then, zinc sulfate, ethylthiocarbamate, ethylthio nitrogen and a frother are added in sequence, stirred and slurried, a roughing operation is performed to obtain a roughing concentrate and a roughing tailing. The roughing tailing is added with ethylthiocarbamate and ethylthio nitrogen for a scavenging operation to obtain a scavenging concentrate and a scavenging tailing. The scavenging concentrate is returned to the roughing operation. The scavenging tailing is added with ethylthiocarbamate for slurrying, and a secondary scavenging operation is performed to obtain a secondary scavenging concentrate and a secondary scavenging tailing. The secondary scavenging concentrate is returned to the primary scavenging operation;

[0035] The primary roughing concentrate is subjected to cyclone classification, and after classification, the sedimentary ore removed by the cyclone is regrinded, and the regrinding product is combined with the cyclone overflow to obtain a mixture, and zinc sulfate and lime are added to the mixture to adjust the slurry and then the mixture is copper-selected, and the pH of the copper-selected slurry of the mixture is 10-11, and the copper-selected concentrate and the copper-selected tailings of the mixture are obtained;

[0036] 2) The copper concentrate tailings and the secondary scavenging tailings of the mixture are combined, and an enhancing active agent, butyl xanthate and a frother are added in sequence. After mixing and slurrying, a mixed roughing is carried out to obtain a primary zinc-sulfur roughing ore and a primary zinc-sulfur roughing tailing. The primary zinc-sulfur roughing ore is subjected to a primary zinc-sulfur concentration to obtain a primary zinc-sulfur concentrated ore and a primary zinc-sulfur concentrated tailing, and the primary zinc-sulfur concentrated tailing is returned to the mixed slurrying operation; the primary zinc-sulfur concentrated ore is subjected to a secondary zinc-sulfur concentration to obtain a zinc-sulfur concentrate and a secondary zinc-sulfur concentrated tailing, and the secondary zinc-sulfur concentrated tailing is returned to the primary mixed roughing operation; butyl xanthate and an enhancing active agent are added to the primary zinc-sulfur roughing tailing, and zinc-sulfur scavenging is carried out after slurrying to obtain a scavenging concentrate and a scavenging tailing, and the scavenging concentrate is returned to the mixed slurrying operation;

[0037] 3) adding lime to the zinc-sulfur concentrate to prepare a slurry, and then performing zinc concentration to obtain zinc concentrated concentrate and zinc concentrated tailings;

[0038] 4) The scavenging tailings and the zinc concentrate tailings are separated by a centrifugal concentrator to obtain centrifuge tailings and separated ore, the separated ore is classified, and the classified +0.045 mm particle size ore is subjected to coarse-grained shaking table gravity selection to obtain coarse-grained gravity-selected tin concentrate, coarse-grained middlings and coarse-grained tailings, and the coarse-grained middlings are subjected to coarse-grained reselection to obtain coarse-grained reselected tin concentrate and coarse-grained reselected tin tailings;

[0039] After classification, the -0.045 mm particle size ore is subjected to fine-grained shaking table gravity selection to obtain fine-grained gravity-selected tin concentrate, fine-grained intermediate ore and fine-grained tailings, and the fine-grained intermediate ore is subjected to fine-grained reselection to obtain fine-grained reselected tin concentrate and fine-grained reselected tin tailings;

[0040] Combining the coarse-grained tin concentrate with the coarse-grained tin concentrate with the re-selected tin concentrate, the fine-grained tin concentrate with the fine-grained tin concentrate to obtain a tin concentrate;

[0041] 5) combining the coarse tailings, coarse re-selected tin tailings, fine tailings and fine re-selected tin tailings, adding sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate and an activator in sequence, and carrying out tin rough selection after slurry mixing to obtain tin rough selection and tin rough selection tailings, adding sodium silicate to the tin rough selection to carry out primary tin selection to obtain primary tin selection ore and primary tin selection tailings, adding sodium silicate to the primary tin selection ore to carry out secondary tin selection to obtain flotation tin concentrate and secondary tin selection tailings, and the secondary tin selection tailings are returned to the primary washing and selection operation; the primary tin selection tailings are returned to the tin rough selection operation; adding an activator to the tin rough selection tailings to carry out a tin scavenging selection to obtain a primary tin scavenging selection and a primary tin scavenging selection tailings, and the primary tin scavenging selection tailings are returned to the tin rough selection operation; adding an activator to the primary tin scavenging selection tailings to carry out secondary tin scavenging selection to obtain secondary tin scavenging selection and secondary tailings, and the secondary tin scavenging selection tailings are returned to the primary tin scavenging selection operation.

[0042] In the step 1), 500 g / t zinc sulfate, 100 g / t ethylthiocarbamate, 70 g / t ethylthiocyanate and 25 g / t foaming agent BK-206 are added in sequence per ton of raw ore, and a roughing is performed after stirring and slurrying;

[0043] Calculated per ton of raw ore, 25g / t ethylthiocarbamate and 30g / t ethylthiocyanate are added to the roughing tailings for a scavenging;

[0044] Based on each ton of raw ore, 30g / t ethionamide is added to the tailings of the first scavenging process to prepare the slurry for the second scavenging process.

[0045] In the above 1), based on each ton of raw ore, 700 g / t zinc sulfate and 800 g / t lime are added to the mixture for slurry preparation and then the mixture is selected.

[0046] Therefore, for every ton of raw ore, 800g / t of enhancing active agent, 20g / t of butyl xanthate and 15g / t of foaming agent BK-206 are added in sequence, and after mixing and slurrying, a mixed roughing is carried out. The enhancing active agent includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.5.

[0047] In the step 2), 80 g / t butyl xanthate and 300 g / t enhancing activator are added to the primary zinc-sulfur roughing tailings per ton of raw ore, and zinc-sulfur scavenging is performed after slurry adjustment.

[0048] In the step 3), 800 g / t of lime is added.

[0049] In the step 4), 500 g / t sulfuric acid, 200 g / t alkyl phosphoric acid, 20 g / t sodium silicate, 100 g / t palladium nitrate and 150 g / t activator are sequentially added per ton of raw ore to prepare slurry for rough tin selection.

[0050] As a preferred technical solution, in the step 4), per ton of raw ore, 50 g / t of the tin roughing tailings is added with an initiator to carry out a tin scavenging operation to obtain a primary tin scavenging operation and a primary tin scavenging tailings, and the primary tin scavenging operation is returned to the tin roughing operation; and 50 g / t of the initiator is added to the primary tin scavenging tailings to carry out a secondary tin scavenging operation.

[0051] Based on each ton of raw ore, 100g / t sodium silicate is added to the tin rough beneficiation to carry out primary tin concentration to obtain primary tin concentrated ore and primary tin concentrated tailings. 50g / t sodium silicate is added to the primary tin concentrated ore to carry out secondary tin concentration to obtain flotation tin concentrate and secondary tin concentrated tailings.

[0052] The activator comprises 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether and octylphenol, and the dosage ratio thereof is 20:45:25:10:2.

[0053] The preparation process of oleic acid sulfate soap is:

[0054] Oleic acid is used as the basic raw material, and concentrated sulfuric acid with a mass ratio of 10% to 20% of oleic acid is added thereto for esterification reaction for 40 to 90 minutes, and 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, and the reaction is carried out for 1 to 1.5 hours to obtain oleic acid sulfated soap.

[0055] Add pine oil, octylphenol and nonylphenol polyoxyethylene ether to the oleic acid sulfated soap according to the above ratio, stir and react at room temperature for 0.5 to 1 hour, and after the reaction is completed, add 2-ethylhexanoic anhydride to the product, stir and mix at room temperature for 0.5 to 1 hour to obtain an activator.

[0056] The final zinc concentrate contained 45.44% zinc and 908.7g / t indium, with an indium recovery rate of 81.94% and a tin recovery rate of 85.26%.

[0057] Embodiment 2:

[0058] The ore was selected from a mining area in Yunnan. The average ore content was 0.56% copper, 3.24% zinc, 10.5% sulfur, 0.84% ​​tin, 10.5% iron, 96.8g / t indium, and 18.1% silicon dioxide. Tin and indium minerals were the main objects of recovery.

[0059] 1) Grinding: after the mixed concentrate is crushed and ground, the grinding fineness is -0.074mm, accounting for 85%. Then, sodium humate, zinc sulfate, ethylthiocarbamate, ethylthiocyanate and acrylonitrile are added in sequence, stirred and slurried, a roughing operation is performed to obtain a roughing concentrate and a roughing tailing. The roughing tailing is added with ethylthiocarbamate and ethylthiocyanate for a scavenging operation to obtain a scavenging concentrate and a scavenging tailing. The scavenging concentrate is returned to the roughing operation. The scavenging tailing is added with ethylthiocarbamate for slurrying, and a secondary scavenging operation is performed to obtain a secondary scavenging concentrate and a secondary scavenging tailing. The secondary scavenging concentrate is returned to the primary scavenging operation;

[0060] The primary roughing concentrate is subjected to cyclone classification, and after classification, the sedimentary ore removed by the cyclone is regrinded, and the regrinding product is combined with the cyclone overflow to obtain a mixture, and zinc sulfate and lime are added to the mixture to adjust the slurry and then the mixture is copper-selected, and the pH of the copper-selected slurry of the mixture is 10-11, and the copper-selected concentrate and the copper-selected tailings of the mixture are obtained;

[0061] 2) The copper concentrate tailings and the secondary scavenging tailings of the mixture are combined, and an enhancing active agent, butyl xanthate and a frother are added in sequence. After mixing and slurrying, a mixed roughing is carried out to obtain a primary zinc-sulfur roughing ore and a primary zinc-sulfur roughing tailing. The primary zinc-sulfur roughing ore is subjected to a primary zinc-sulfur concentration to obtain a primary zinc-sulfur concentrated ore and a primary zinc-sulfur concentrated tailing, and the primary zinc-sulfur concentrated tailing is returned to the mixed slurrying operation; the primary zinc-sulfur concentrated ore is subjected to a secondary zinc-sulfur concentration to obtain a zinc-sulfur concentrate and a secondary zinc-sulfur concentrated tailing, and the secondary zinc-sulfur concentrated tailing is returned to the primary mixed roughing operation; butyl xanthate and an enhancing active agent are added to the primary zinc-sulfur roughing tailing, and zinc-sulfur scavenging is carried out after slurrying to obtain a scavenging concentrate and a scavenging tailing, and the scavenging concentrate is returned to the mixed slurrying operation;

[0062] 3) adding lime to the zinc-sulfur concentrate to prepare a slurry, and then performing zinc concentration to obtain zinc concentrated concentrate and zinc concentrated tailings;

[0063] 4) The scavenging tailings and the zinc concentrate tailings are separated by a centrifugal concentrator to obtain centrifuge tailings and separated ore, the separated ore is classified, and the classified +0.045 mm particle size ore is subjected to coarse-grained shaking table gravity selection to obtain coarse-grained gravity-selected tin concentrate, coarse-grained middlings and coarse-grained tailings, and the coarse-grained middlings are subjected to coarse-grained reselection to obtain coarse-grained reselected tin concentrate and coarse-grained reselected tin tailings;

[0064] After classification, the -0.045 mm particle size ore is subjected to fine-grained shaking table gravity selection to obtain fine-grained gravity-selected tin concentrate, fine-grained intermediate ore and fine-grained tailings, and the fine-grained intermediate ore is subjected to fine-grained reselection to obtain fine-grained reselected tin concentrate and fine-grained reselected tin tailings;

[0065] Combining the coarse-grained tin concentrate with the coarse-grained tin concentrate with the re-selected tin concentrate, the fine-grained tin concentrate with the fine-grained tin concentrate to obtain a tin concentrate;

[0066] 5) combining the coarse tailings, coarse re-selected tin tailings, fine tailings and fine re-selected tin tailings, adding sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate and an activator in sequence, and carrying out tin rough selection after slurry mixing to obtain tin rough selection and tin rough selection tailings, adding sodium silicate to the tin rough selection to carry out primary tin selection to obtain primary tin selection ore and primary tin selection tailings, adding sodium silicate to the primary tin selection ore to carry out secondary tin selection to obtain flotation tin concentrate and secondary tin selection tailings, and the secondary tin selection tailings are returned to the primary washing and selection operation; the primary tin selection tailings are returned to the tin rough selection operation; adding an activator to the tin rough selection tailings to carry out a tin scavenging selection to obtain a primary tin scavenging selection and a primary tin scavenging selection tailings, and the primary tin scavenging selection tailings are returned to the tin rough selection operation; adding an activator to the primary tin scavenging selection tailings to carry out secondary tin scavenging selection to obtain secondary tin scavenging selection and secondary tailings, and the secondary tin scavenging selection tailings are returned to the primary tin scavenging selection operation.

[0067] In the step 1), 500 g / t zinc sulfate, 100 g / t ethylthiocarbamate, 70 g / t ethylthiocyanate and 25 g / t foaming agent BK-206 are added in sequence per ton of raw ore, and a roughing is performed after stirring and slurrying;

[0068] Calculated per ton of raw ore, 25g / t ethylthiocarbamate and 30g / t ethylthiocyanate are added to the roughing tailings for a scavenging;

[0069] Based on each ton of raw ore, 30g / t ethionamide is added to the tailings of the first scavenging process to prepare the slurry for the second scavenging process.

[0070] In the above 1), based on each ton of raw ore, 700 g / t zinc sulfate and 800 g / t lime are added to the mixture for slurry preparation and then the mixture is selected.

[0071] Therefore, for every ton of raw ore, 900g / t of enhancing active agent, 20g / t of butyl xanthate and 20g / t of foaming agent BK-206 are added in sequence, and after mixing and slurrying, a mixed roughing is carried out. The enhancing active agent includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.5.

[0072] In the step 2), 80 g / t butyl xanthate and 300 g / t enhancing activator are added to the primary zinc-sulfur roughing tailings per ton of raw ore, and zinc-sulfur scavenging is performed after slurry adjustment.

[0073] In the step 3), 700 g / t of lime is added.

[0074] In the step 4), 500 g / t sulfuric acid, 200 g / t alkyl phosphoric acid, 20 g / t sodium silicate, 100 g / t palladium nitrate and 180 g / t activator are sequentially added per ton of raw ore to prepare slurry for rough tin selection.

[0075] In the step 4), per ton of raw ore, 60 g / t of the tin roughing tailings are added to carry out a tin scavenging, to obtain a primary tin scavenging and a primary tin scavenging tailings, and the primary tin scavenging is returned to the tin roughing operation; and 60 g / t of the primary tin scavenging tailings are added to carry out a secondary tin scavenging.

[0076] Based on each ton of raw ore, 100g / t sodium silicate is added to the tin rough beneficiation to carry out primary tin concentration to obtain primary tin concentrated ore and primary tin concentrated tailings. 50g / t sodium silicate is added to the primary tin concentrated ore to carry out secondary tin concentration to obtain flotation tin concentrate and secondary tin concentrated tailings.

[0077] The activator comprises 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether and octylphenol, and the dosage ratio thereof is 20:45:25:10:2.

[0078] The preparation process of oleic acid sulfate soap is:

[0079] Oleic acid is used as the basic raw material, and concentrated sulfuric acid with a mass ratio of 10% to 20% of oleic acid is added thereto for esterification reaction for 40 to 90 minutes, and 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, and the reaction is carried out for 1 to 1.5 hours to obtain oleic acid sulfated soap.

[0080] Add pine oil, octylphenol and nonylphenol polyoxyethylene ether to the oleic acid sulfated soap according to the above ratio, stir and react at room temperature for 0.5 to 1 hour, and after the reaction is completed, add 2-ethylhexanoic anhydride to the product, stir and mix at room temperature for 0.5 to 1 hour to obtain an activator.

[0081] Among them, the recovery rate of indium is 82.43% and the recovery rate of tin is 85.48%.

[0082] Embodiment 3:

[0083] The ore was selected from a mining area in Yunnan. The average ore content was 0.92% copper, 1.85% zinc, 10.3% sulfur, 0.84% ​​tin, 14.4% iron, 110.5g / t indium, and 17.5% silicon dioxide. Tin and indium minerals were the main objects of recovery.

[0084] 1) Grinding: after the mixed concentrate is crushed and ground, the grinding fineness is -0.074mm, accounting for 80%. Then, sodium humate, zinc sulfate, ethylthiocarbamate, ethylthiocyanate and acrylonitrile are added in sequence, stirred and slurried, a roughing operation is performed to obtain a roughing concentrate and a roughing tailing. The roughing tailing is added with ethylthiocarbamate and ethylthiocyanate for a scavenging operation to obtain a scavenging concentrate and a scavenging tailing. The scavenging concentrate is returned to the roughing operation. The scavenging tailing is added with ethylthiocarbamate for slurrying, and a secondary scavenging operation is performed to obtain a secondary scavenging concentrate and a secondary scavenging tailing. The secondary scavenging concentrate is returned to the primary scavenging operation;

[0085] The primary roughing concentrate is subjected to cyclone classification, and after classification, the sedimentary ore removed by the cyclone is regrinded, and the regrinding product is combined with the cyclone overflow to obtain a mixture, and zinc sulfate and lime are added to the mixture to adjust the slurry and then the mixture is copper-selected, and the pH of the copper-selected slurry of the mixture is 10-11, and the copper-selected concentrate and the copper-selected tailings of the mixture are obtained;

[0086] 2) The copper concentrate tailings and the secondary scavenging tailings of the mixture are combined, and an enhancing active agent, butyl xanthate and a frother are added in sequence. After mixing and slurrying, a mixed roughing is carried out to obtain a primary zinc-sulfur roughing ore and a primary zinc-sulfur roughing tailing. The primary zinc-sulfur roughing ore is subjected to a primary zinc-sulfur concentration to obtain a primary zinc-sulfur concentrated ore and a primary zinc-sulfur concentrated tailing, and the primary zinc-sulfur concentrated tailing is returned to the mixed slurrying operation; the primary zinc-sulfur concentrated ore is subjected to a secondary zinc-sulfur concentration to obtain a zinc-sulfur concentrate and a secondary zinc-sulfur concentrated tailing, and the secondary zinc-sulfur concentrated tailing is returned to the primary mixed roughing operation; butyl xanthate and an enhancing active agent are added to the primary zinc-sulfur roughing tailing, and zinc-sulfur scavenging is carried out after slurrying to obtain a scavenging concentrate and a scavenging tailing, and the scavenging concentrate is returned to the mixed slurrying operation;

[0087] 3) adding lime to the zinc-sulfur concentrate to prepare a slurry, and then performing zinc concentration to obtain zinc concentrated concentrate and zinc concentrated tailings;

[0088] 4) The scavenging tailings and the zinc concentrate tailings are separated by a centrifugal concentrator to obtain centrifuge tailings and separated ore, the separated ore is classified, and the classified +0.045 mm particle size ore is subjected to coarse-grained shaking table gravity selection to obtain coarse-grained gravity-selected tin concentrate, coarse-grained middlings and coarse-grained tailings, and the coarse-grained middlings are subjected to coarse-grained reselection to obtain coarse-grained reselected tin concentrate and coarse-grained reselected tin tailings;

[0089] After classification, the -0.045 mm particle size ore is subjected to fine-grained shaking table gravity selection to obtain fine-grained gravity-selected tin concentrate, fine-grained intermediate ore and fine-grained tailings, and the fine-grained intermediate ore is subjected to fine-grained reselection to obtain fine-grained reselected tin concentrate and fine-grained reselected tin tailings;

[0090] Combining the coarse-grained tin concentrate with the coarse-grained tin concentrate with the re-selected tin concentrate, the fine-grained tin concentrate with the fine-grained tin concentrate to obtain a tin concentrate;

[0091] 5) combining the coarse tailings, coarse re-selected tin tailings, fine tailings and fine re-selected tin tailings, adding sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate and an activator in sequence, and carrying out tin rough selection after slurry mixing to obtain tin rough selection and tin rough selection tailings, adding sodium silicate to the tin rough selection to carry out primary tin selection to obtain primary tin selection ore and primary tin selection tailings, adding sodium silicate to the primary tin selection ore to carry out secondary tin selection to obtain flotation tin concentrate and secondary tin selection tailings, and the secondary tin selection tailings are returned to the primary washing and selection operation; the primary tin selection tailings are returned to the tin rough selection operation; adding an activator to the tin rough selection tailings to carry out a tin scavenging selection to obtain a primary tin scavenging selection and a primary tin scavenging selection tailings, and the primary tin scavenging selection tailings are returned to the tin rough selection operation; adding an activator to the primary tin scavenging selection tailings to carry out secondary tin scavenging selection to obtain secondary tin scavenging selection and secondary tailings, and the secondary tin scavenging selection tailings are returned to the primary tin scavenging selection operation.

[0092] In the step 1), 500 g / t zinc sulfate, 100 g / t ethylthiocarbamate, 70 g / t ethylthiocyanate and 25 g / t foaming agent BK-206 are added in sequence per ton of raw ore, and a roughing is performed after stirring and slurrying;

[0093] Calculated per ton of raw ore, 25g / t ethylthiocarbamate and 30g / t ethylthiocyanate are added to the roughing tailings for a scavenging;

[0094] Based on each ton of raw ore, 30g / t ethionamide is added to the tailings of the first scavenging process to prepare the slurry for the second scavenging process.

[0095] In the above 1), based on each ton of raw ore, 700 g / t zinc sulfate and 800 g / t lime are added to the mixture for slurry preparation and then the mixture is selected.

[0096] Therefore, for every ton of raw ore, 1000g / t of enhancing active agent, 20g / t of butyl xanthate and 20g / t of foaming agent BK-206 are added in sequence, and after mixing and slurrying, a mixed roughing is carried out. The enhancing active agent includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.5.

[0097] In the step 2), 80 g / t butyl xanthate and 300 g / t enhancing activator are added to the primary zinc-sulfur roughing tailings per ton of raw ore, and zinc-sulfur scavenging is performed after slurry adjustment.

[0098] In the step 3), 600 g / t of lime is added.

[0099] In the step 4), 500 g / t sulfuric acid, 200 g / t alkyl phosphoric acid, 20 g / t sodium silicate, 100 g / t palladium nitrate and 200 g / t activator are sequentially added per ton of raw ore to prepare slurry for rough tin selection.

[0100] In the step 4), per ton of raw ore, 70 g / t of the tin roughing tailings are added with the initiator for a tin scavenging operation to obtain a primary tin scavenging operation and a primary tin scavenging tailings, and the primary tin scavenging operation is returned to the tin roughing operation; and 70 g / t of the initiator is added to the primary tin scavenging tailings for a secondary tin scavenging operation.

[0101] Based on each ton of raw ore, 100g / t sodium silicate is added to the tin rough beneficiation to carry out primary tin concentration to obtain primary tin concentrated ore and primary tin concentrated tailings. 50g / t sodium silicate is added to the primary tin concentrated ore to carry out secondary tin concentration to obtain flotation tin concentrate and secondary tin concentrated tailings.

[0102] The activator comprises 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether and octylphenol, and the dosage ratio thereof is 20:45:25:10:2.

[0103] The preparation process of oleic acid sulfate soap is:

[0104] Oleic acid is used as the basic raw material, and concentrated sulfuric acid with a mass ratio of 10% to 20% of oleic acid is added thereto for esterification reaction for 40 to 90 minutes, and 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, and the reaction is carried out for 1 to 1.5 hours to obtain oleic acid sulfated soap.

[0105] Add pine oil, octylphenol and nonylphenol polyoxyethylene ether to the oleic acid sulfated soap according to the above ratio, stir and react at room temperature for 0.5 to 1 hour, and after the reaction is completed, add 2-ethylhexanoic anhydride to the product, stir and mix at room temperature for 0.5 to 1 hour to obtain an activator.

[0106] Among them, the recovery rate of indium operation is 83.05%, and the recovery rate of tin operation is 85.53%. It can be seen that the use of this invention can not only improve the efficiency of mineral processing, but also efficiently recover resources such as zinc and indium.

[0107] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for beneficiating indium and tin in mixed concentrate after ore material recovery, characterized in that: The following steps are involved: 1) Grinding: after the mixed concentrate is crushed and ground, the grinding fineness is -0.074mm, accounting for 80-85%. Then, zinc sulfate, ethylthiocarbamate, ethylthio nitrogen and a frother are added in sequence, stirred and slurried, a roughing is performed to obtain a roughing concentrate and a roughing tailing. The roughing tailing is added with ethylthiocarbamate and ethylthio nitrogen for a scavenging to obtain a scavenging concentrate and a scavenging tailing. The scavenging concentrate is returned to the roughing operation. The scavenging tailing is added with ethylthiocarbamate for slurrying, and a secondary scavenging is performed to obtain a secondary scavenging concentrate and a secondary scavenging tailing. The secondary scavenging concentrate is returned to the primary scavenging operation; The primary roughing concentrate is subjected to cyclone classification, and after classification, the sedimentary ore removed by the cyclone is regrinded, and the regrinding product is combined with the cyclone overflow to obtain a mixture, and zinc sulfate and lime are added to the mixture to adjust the slurry and then the mixture is copper-selected, and the pH of the copper-selected slurry of the mixture is 10-11, and the copper-selected concentrate and the copper-selected tailings of the mixture are obtained; 2) The copper concentrate tailings and the secondary scavenging tailings of the mixture are combined, and an enhancing active agent, butyl xanthate and a frother are added in sequence. After mixing and slurrying, a mixed roughing is carried out to obtain a primary zinc-sulfur roughing ore and a primary zinc-sulfur roughing tailing. The primary zinc-sulfur roughing ore is subjected to a primary zinc-sulfur concentration to obtain a primary zinc-sulfur concentrated ore and a primary zinc-sulfur concentrated tailing, and the primary zinc-sulfur concentrated tailing is returned to the mixed slurrying operation; the primary zinc-sulfur concentrated ore is subjected to a secondary zinc-sulfur concentration to obtain a zinc-sulfur concentrate and a secondary zinc-sulfur concentrated tailing, and the secondary zinc-sulfur concentrated tailing is returned to the primary mixed roughing operation; butyl xanthate and an enhancing active agent are added to the primary zinc-sulfur roughing tailing, and zinc-sulfur scavenging is carried out after slurrying to obtain a scavenging concentrate and a scavenging tailing, and the scavenging concentrate is returned to the mixed slurrying operation; 3) adding lime to the zinc-sulfur concentrate to prepare a slurry, and then performing zinc concentration to obtain zinc concentrated concentrate and zinc concentrated tailings; 4) The scavenging tailings and the zinc concentrate tailings are separated by a centrifugal concentrator to obtain centrifuge tailings and separated ore, the separated ore is classified, and the classified +0.045 mm particle size ore is subjected to coarse-grained shaking table gravity selection to obtain coarse-grained gravity-selected tin concentrate, coarse-grained middlings and coarse-grained tailings, and the coarse-grained middlings are subjected to coarse-grained reselection to obtain coarse-grained reselected tin concentrate and coarse-grained reselected tin tailings; After classification, the -0.045 mm particle size ore is subjected to fine-grained shaking table gravity selection to obtain fine-grained gravity-selected tin concentrate, fine-grained intermediate ore and fine-grained tailings, and the fine-grained intermediate ore is subjected to fine-grained reselection to obtain fine-grained reselected tin concentrate and fine-grained reselected tin tailings; Combining the coarse-grained tin concentrate with the coarse-grained tin concentrate with the re-selected tin concentrate, the fine-grained tin concentrate with the fine-grained tin concentrate to obtain a tin concentrate; 5) combining the coarse tailings, coarse re-selected tin tailings, fine tailings and fine re-selected tin tailings, adding sulfuric acid, alkyl phosphoric acid, sodium silicate, palladium nitrate and an activator in sequence, and carrying out tin rough selection after slurry mixing to obtain tin rough selection and tin rough selection tailings, adding sodium silicate to the tin rough selection to carry out primary tin selection to obtain primary tin selection ore and primary tin selection tailings, adding sodium silicate to the primary tin selection ore to carry out secondary tin selection to obtain flotation tin concentrate and secondary tin selection tailings, and the secondary tin selection tailings are returned to the primary washing and selection operation; the primary tin selection tailings are returned to the tin rough selection operation; adding an activator to the tin rough selection tailings to carry out a tin scavenging selection to obtain a primary tin scavenging selection and a primary tin scavenging selection tailings, and the primary tin scavenging selection tailings are returned to the tin rough selection operation; adding an activator to the primary tin scavenging selection tailings to carry out secondary tin scavenging selection to obtain secondary tin scavenging selection and secondary tailings, and the secondary tin scavenging selection tailings are returned to the primary tin scavenging selection operation.

2. The method for beneficiating indium tin in mixed concentrate after ore material recovery according to claim 1, characterized in that: In the step 1), 500 g / t zinc sulfate, 100 g / t ethylthiocarbamate, 70 g / t ethylthiocyanate and 25 g / t foaming agent are added in sequence per ton of raw ore, and a roughing is performed after stirring and slurrying; Calculated per ton of raw ore, 25g / t ethylthiocarbamate and 30g / t ethylthiocyanate are added to the roughing tailings for a scavenging; Based on each ton of raw ore, 30g / t ethionamide is added to the tailings of the first scavenging process to prepare the slurry for the second scavenging process.

3. The method for beneficiating indium tin in mixed concentrate after ore material recovery according to claim 2, characterized in that: In the above 1), based on each ton of raw ore, 700 g / t zinc sulfate and 800 g / t lime are added to the mixture for slurry preparation and then the mixture is concentrating.

4. The method for beneficiating indium tin in mixed concentrate after ore material recovery according to claim 1, characterized in that: In the above 2), 800-1000 g / t of an enhancing active agent, 20 g / t of butyl xanthate and 15-20 g / t of a foaming agent are added in sequence per ton of raw ore, and after mixing and slurrying, a mixed roughing is performed. The enhancing active agent includes copper sulfate and ammonium bicarbonate in a mass ratio of 2:1.

5.

5. The method for beneficiating indium and tin in mixed concentrate after ore material recovery according to claim 1, characterized in that: In the step 2), 80 g / t butyl xanthate and 300 g / t enhancing activator are added to the primary zinc-sulfur roughing tailings per ton of raw ore, and zinc-sulfur scavenging is performed after slurry adjustment.

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

7. A method for beneficiating indium and tin in mixed concentrate after ore material recovery as claimed in claim 6, characterized in that: In the step 4), per ton of raw ore, 50-70 g / t of the tin roughing tailings are added with an initiator to carry out a tin scavenging operation to obtain a primary tin scavenging operation and a primary tin scavenging tailings, and the primary tin scavenging operation is returned to the tin roughing operation; and 50-70 g / t of the initiator is added to the primary tin scavenging tailings to carry out a secondary tin scavenging operation.

8. The method for beneficiating indium and tin in mixed concentrate after ore material recovery according to claim 1, characterized in that: Based on each ton of raw ore, 100g / t sodium silicate is added to the tin rough beneficiation to carry out primary tin concentration to obtain primary tin concentrated ore and primary tin concentrated tailings. 50g / t sodium silicate is added to the primary tin concentrated ore to carry out secondary tin concentration to obtain flotation tin concentrate and secondary tin concentrated tailings.

9. A method for beneficiating indium tin in mixed concentrate after ore material recovery according to claim 6 or 7, characterized in that: The activator comprises 2-ethylhexanoic anhydride, oleic acid sulfate soap, pine oil, nonylphenol polyoxyethylene ether and octylphenol, and the dosage ratio thereof is 20:45:25:10:2.

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