A separation method for a mixed concentrate of tungsten, tin, bismuth and sulfur

Abstract

The present invention provides a method for separating tungsten, tin, bismuth, and sulfur mixed concentrates. The method first grinds and slurries the tungsten, tin, bismuth, and sulfur mixed concentrate. The concentrate then undergoes a series of processes, including bismuth flotation (one coarse, two fine, two sweeps), sulfur flotation (one coarse, two fine, one sweep), and tungsten flotation (one coarse, two fine, one sweep). Finally, the concentrates are separated by weak magnetic separation of the bismuth concentrate and shaking table separation of the flotation tungsten tailings to obtain tungsten, tin, bismuth, and sulfur concentrates. By utilizing the coordinated operation of various reagents, the present invention not only reduces the amount of ore processed, the amount of equipment required, the process flow, and reagent costs, but also effectively separates valuable minerals such as tungsten, tin, bismuth, and sulfur from the tungsten, tin, bismuth, and sulfur mixed concentrate, yielding a high-grade, high-recovery concentrate product.

Description

Technical Field

[0001] The present invention belongs to the technical field of ore resource utilization and more specifically relates to a method for separating tungsten, tin, bismuth and sulfur mixed concentrate. Background Art

[0002] Polymetallic deposits dominated by tungsten and tin, with associated bismuth and sulfur, are characterized by low metal grades for both the primary and associated metals, making them difficult-to-process mineral resources. Sequentially separating one or several valuable minerals from the raw ore results in large ore volumes, extensive equipment, complex reagent systems, complex process flows, and high processing costs, significantly limiting the development of this resource. Furthermore, tungsten-tin ores contain numerous associated valuable minerals. While tin is generally more valuable than a single nonferrous metal, the combined value of the associated metals is often higher than that of tin. Therefore, only comprehensive recovery of all the valuable metals can maximize the utilization of this deposit's resources.

[0003] The method of obtaining tungsten-tin-bismuth-sulfur mixed concentrate by coarse grinding (-0.074mm accounting for less than 60%) and table flotation (or shaking table gravity separation) of polymetallic ore deposits mainly composed of tungsten and tin and associated bismuth and sulfur can not only discard a large amount of waste rock, reduce the energy consumption of mineral processing, greatly reduce the amount of subsequent separated minerals, the number of equipment and the amount of reagents used, and significantly improve the processing capacity of the mineral processing plant without a large amount of capital, but also is conducive to the control of the subsequent grinding process and the improvement of mineral processing indicators, reduce the amount of fine tailings to be processed, reduce the pollution of fine tailings to the environment, and further ensure a higher recovery rate of valuable minerals.

[0004] Although the method of obtaining tungsten, tin, bismuth and sulfur mixed concentrate by table flotation or shaking table gravity separation guarantees the recovery rate of tungsten, tin, bismuth and sulfur to a certain extent, the existing method of separating the tungsten, tin, bismuth and sulfur mixed concentrate still leads to a large loss of tungsten, tin and bismuth, which is not conducive to the comprehensive recovery of this resource. Therefore, it is quite necessary to find a method that can effectively separate the tungsten, tin, bismuth and sulfur mixed concentrate to produce high-grade and high-recovery valuable elements for the recovery of tungsten, tin, bismuth and sulfur. Summary of the Invention

[0005] In view of the above-mentioned deficiencies in the prior art, the present invention aims to provide a method for separating tungsten-tin-bismuth-sulfur mixed concentrate to achieve efficient recovery of tungsten, tin, bismuth and sulfur.

[0006] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0007] The present invention provides a method for separating a tungsten-tin-bismuth-sulfur mixed concentrate, comprising the following steps:

[0008] S1. Bismuth flotation: After grinding and slurrying the tungsten-tin-bismuth-sulfur mixed concentrate, a regulator, a collector, and a frother are sequentially added to perform a roughing process to obtain a roughing concentrate and a bismuth flotation roughing tailing; a regulator and a frother are added to the roughing concentrate to perform a primary concentration process to obtain a primary concentrated concentrate and a primary concentrated tailing; the primary concentrated concentrate is subjected to a secondary blank concentration process to obtain a flotation bismuth concentrate and a secondary concentrated tailing, and the flotation bismuth concentrate is subjected to weak magnetic separation to obtain a bismuth concentrate and a high-iron sulfur concentrate; a collector and a frother are added to the bismuth flotation roughing tailing to perform a scavenging process to obtain a primary scavenging concentrate and a primary scavenging tailing; a collector and a frother are added to the primary scavenging tailing to perform a secondary scavenging process to obtain a secondary scavenging concentrate and a bismuth flotation tailing;

[0009] S2 flotation sulfur: sulfuric acid, butyl xanthate, and 2# oil were sequentially added to the floating bismuth tailings obtained in S1 to perform a roughing operation to obtain a rougher concentrate and a floating sulfur rougher tailings; butyl xanthate and 2# oil were added to the rougher concentrate to perform a concentration operation to obtain a concentrated concentrate and a concentrated tailings; the concentrated concentrate was subjected to a secondary blank concentration operation to obtain flotation pyrite and a secondary concentrated tailings, and the flotation pyrite and the high-iron sulfur concentrate obtained in S1 were combined into a sulfur concentrate; butyl xanthate and 2# oil were added to the floating sulfur rougher tailings to perform a scavenging operation to obtain a scavenging concentrate and a floating sulfur tailings;

[0010] S3. Tungsten flotation: adding a regulator, an activator, and a collector to the flotation sulfur tailings obtained in S2 in sequence to perform a roughing operation to obtain a roughing concentrate and flotation tungsten roughing tailings; adding a regulator to the roughing concentrate to perform a primary concentration operation to obtain a primary concentration concentrate and a primary concentration tailings; then performing a secondary blank concentration operation on the primary concentration concentrate to obtain a tungsten concentrate and a secondary concentration tailings; adding a collector to the flotation tungsten roughing tailings to perform a scavenging operation to obtain a primary scavenging concentrate and flotation tungsten tailings;

[0011] S4. Reselection of tin: The floating tungsten tailings obtained in S3 are sorted on a shaking table to obtain tin concentrate, tin sub-concentrate and tailings.

[0012] Tungsten-tin-bismuth-sulfur mixed concentrate is obtained from polymetallic deposits mainly composed of tungsten and tin, with associated bismuth and sulfur, by coarse grinding (-0.074mm accounting for less than 60%) and then through table flotation or shaking table gravity separation.

[0013] The present invention provides a method for separating a tungsten-tin-bismuth-sulfur mixed concentrate. This method, based on the natural differences in the properties of the valuable minerals in the tungsten-tin-bismuth-sulfur mixed concentrate, amplifies these differences through a specific reagent system, achieving efficient separation of valuable minerals such as tungsten, tin, bismuth, and sulfur from the tungsten-tin-bismuth-sulfur mixed concentrate. This method is suitable for separating tungsten-tin-bismuth-sulfur mixed concentrates, and is particularly suitable for separating tungsten-tin-bismuth-sulfur mixed concentrates obtained by coarse grinding (less than 60% of the bismuth content is -0.074 mm) and table flotation (or shaking table gravity separation) of low-grade tungsten-tin ores containing low-grade valuable metals, where the bismuth minerals are primarily bismuth sulfide or natural bismuth, the sulfur minerals are primarily high-iron sulfur concentrates and pyrite, the tungsten minerals are primarily scheelite, and the tin minerals are primarily cassiterite.

[0014] The flotation bismuth concentrate, sulfur concentrate, tungsten concentrate and tin concentrate obtained in steps S1 to S4 are enriched with tungsten, tin, bismuth and sulfur, while the tailings obtained in step S4 contain only a small amount of low-grade tungsten, tin, bismuth and sulfur.

[0015] Preferably, the grinding in S1 is grinding the tungsten, tin, bismuth and sulfur mixed concentrate to -0.074 mm, accounting for 75-90%.

[0016] Preferably, the slurry preparation in S1 is to prepare the tungsten, tin, bismuth and sulfur mixed concentrate after grinding to a slurry concentration of 30-40% (w / v), and most preferably 35% (w / v).

[0017] Preferably, the adjusting agent in S1 is a mixture of lime and water glass.

[0018] Further preferably, the mass ratio of the lime to water glass is 0.8-1.2:0.8-1.2.

[0019] Most preferably, the mass ratio of the lime to water glass is 1:1.

[0020] Preferably, the collector in S1 is a mixture of butylammonium black medicine and Y89 yellow medicine.

[0021] More preferably, the mass ratio of the butyl ammonium black drug to the Y89 xanthate is 1.8-2.2:0.8-1.2.

[0022] Most preferably, the mass ratio of the butylammonium black drug to the Y89 xanthate is 2:1.

[0023] Preferably, the foaming agent in S1 is a mixture of terpene alcohol and polypropylene glycol alkyl ether, or a mixture of methyl amyl alcohol and polypropylene glycol alkyl ether.

[0024] More preferably, the mass ratio of the terpene alcohol to the polypropylene glycol alkyl ether is 1.8-2.2:0.8-1.2, and most preferably 2:1.

[0025] More preferably, the mass ratio of the methyl pentanol to the polypropylene glycol alkyl ether is 1.8-2.2:0.8-1.2, and most preferably 2:1.

[0026] Preferably, the magnetic field strength used in the weak magnetic separation in S1 is 0.3-0.45T.

[0027] Preferably, the adjusting agent in S3 is a mixture of sodium silicate, sodium hexametaphosphate and aluminum sulfate.

[0028] More preferably, the mass ratio of the sodium silicate, sodium hexametaphosphate, and aluminum sulfate is 0.8-1.2:1.8-2.2:0.8-1.2.

[0029] Most preferably, the mass ratio of the sodium silicate, sodium hexametaphosphate and aluminum sulfate is 1:2:1.

[0030] Preferably, the activator in S3 is copper chloride.

[0031] Preferably, the collector in S3 is benzohydroxamic acid and C 7-9 A mixture of alkyl hydroxamic acids.

[0032] Further preferably, the benzohydroxamic acid and C 7-9 The mass ratio of alkyl hydroxamic acid is 3.8-4.2:0.8-1.2.

[0033] Most preferably, the benzohydroxamic acid and C 7-9 The mass ratio of alkyl hydroxamic acid is 4:1.

[0034] Preferably, the specific process of flotation of bismuth in S1 is: to each ton of tungsten-tin-bismuth-sulfur mixed concentrate after grinding and slurrying, 2000-4000 grams of adjusting agent, 50-80 grams of collecting agent, and 20-30 grams of foaming agent are sequentially added to perform a roughing process to obtain a roughing concentrate and a flotation bismuth roughing tailing; 500-1000 grams of adjusting agent and 10-20 grams of foaming agent are added to the roughing concentrate to perform a concentration process to obtain a concentrated concentrate and a concentrated tailing; and then The primary concentrated concentrate is subjected to secondary blank concentration to obtain flotation bismuth concentrate and secondary concentrated tailings. The flotation bismuth concentrate is subjected to weak magnetic separation to obtain bismuth concentrate and high iron sulfur concentrate. 10 to 30 grams of collector and 10 to 20 grams of frother are added to the flotation bismuth roughing tailings to perform a primary scavenging selection to obtain a primary scavenging concentrate and a primary scavenging tailings. 5 to 15 grams of collector and 5 to 10 grams of frother are added to the primary scavenging tailings to perform a secondary scavenging selection to obtain a secondary scavenging concentrate and flotation bismuth tailings.

[0035] S1 adopts a preferential bismuth flotation process, which greatly simplifies the process flow and reagent system. In addition, since bismuth minerals and high-iron sulfur concentrates have better floatability than pyrite, if they are inhibited by inhibitors, the difficulty of their activation will increase significantly, and the amount of activation reagents required will increase significantly. Therefore, it is necessary to use a highly selective collector to carry out preferential flotation. This not only ensures the high grade and high recovery rate of bismuth, but also utilizes the natural strong magnetism of high-iron sulfur concentrate to separate it from the bismuth concentrate by weak magnetic separation, ensuring a high recovery rate of sulfur, while creating conditions for subsequent tungsten and tin selection.

[0036] Preferably, the flotation sulfur described in S2 is calculated based on the tungsten, tin, bismuth and sulfur mixed concentrate after grinding and slurrying per ton of S1, and its specific process is: 2000-5000 g / ton of sulfuric acid, 60-100 g / ton of butyl xanthate and 10-30 g / ton of 2# oil are added to the floating bismuth tailings obtained in S1 in sequence to perform a roughing process to obtain a roughing concentrate and a floating sulfur roughing tailings; 10-20 g / ton of butyl xanthate and 5-10 g / ton of 2# oil are added to the roughing concentrate to perform a concentration process to obtain a concentrated concentrate and a concentrated tailings; the concentrated concentrate is subjected to a secondary blank concentration process to obtain flotation pyrite and a secondary concentration tailings, and the flotation pyrite and the high-iron sulfur concentrate obtained in S1 are combined into a sulfur concentrate; 15-20 g / ton of butyl xanthate and 5-10 g / ton of 2# oil are added to the floating sulfur roughing tailings to perform a scavenging process to obtain a scavenging concentrate and a floating sulfur tailings.

[0037] Preferably, the flotation tungsten described in S3 is calculated based on the tungsten, tin, bismuth and sulfur mixed concentrate after grinding and slurrying in S1 per ton, and its specific process is: adding 400-800 g / ton of adjusting agent, 200-600 g / ton of activating agent and 400-800 g / ton of collector to the floating sulfur tailings obtained in S2 in sequence to perform a roughing selection to obtain a roughing concentrate and a floating tungsten roughing tailings; adding 200-600 g / ton of adjusting agent to the roughing concentrate to perform a concentration to obtain a concentrated concentrate and a concentrated tailings; then performing a secondary blank concentration on the concentrated concentrate to obtain a tungsten concentrate and a secondary concentrated tailings; adding 80-140 g / ton of collector to the floating tungsten roughing tailings to perform a scavenging selection to obtain a scavenging concentrate and a floating tungsten tailings.

[0038] The present invention has the following beneficial effects:

[0039] 1. The present invention conducts targeted research on the characteristics of tungsten-tin-bismuth-sulfur mixed concentrate, specifically controls the type and amount of reagents used in each link of the separation method, and cooperates with the specific settings of the process operation links and parameters in the separation process. The entire process is taken as a whole, and each link coordinates and influences each other. During the flotation process, not only sulfide ores and tungsten minerals with a specific gravity close to that of tin can be removed, but also fine-grained minerals that will interfere with the shaking table surface can be simultaneously removed, ultimately realizing the comprehensive recovery of the valuable elements tungsten, tin, bismuth, and sulfur in the tungsten-tin-bismuth-sulfur mixed concentrate.

[0040] 2. The reagent system of each operation in the method of the present invention has little impact on the next operation, and there is no need to add too much reagent to eliminate the impact of the previous operation. It not only creates a good separation environment for the next operation, but also reduces the amount of reagent used.

[0041] 3. The process of flotation first and gravity separation later in the present invention avoids the concentration and dehydration of tailings in each operation, reduces the use of dehydration equipment and transportation equipment, and ensures the smooth flow of the entire process. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is a schematic diagram of the process for separating the tungsten, tin, bismuth and sulfur mixed concentrate in Example 1. DETAILED DESCRIPTION

[0043] The present invention will be further described below with reference to the accompanying drawings and specific examples, but the examples do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0044] Unless otherwise specified, the reagents and materials used in the following examples were commercially available.

[0045] Example 1 A method for separating tungsten, tin, bismuth and sulfur mixed concentrate

[0046] 1. Minerals

[0047] This example uses a low-grade tungsten-tin ore from Yunnan as an example. After coarse grinding (within 60% of -0.074 mm) and table flotation, a tungsten-tin-bismuth-sulfur mixed concentrate with a Sn grade of 0.79%, a WO3 grade of 1.10%, a Bi grade of 0.51%, and a S grade of 9.75% is obtained.

[0048] 2. Separation Methods and Results

[0049] S1. Bismuth flotation: Grind the tungsten-tin-bismuth-sulfur mixed concentrate to -0.074mm, accounting for 75%, and then adjust the pulp to a concentration of 40% (w / v). Add the adjusting agent, collector, and frother to each ton of pulp according to the reagents and dosages in Table 1 to perform a roughing process to obtain a roughing concentrate and a roughing tailing with bismuth flotation. Add the adjusting agent and frother to the roughing concentrate to perform a concentration process to obtain a concentrated concentrate and a concentrated tailing. Perform a secondary blank concentration on the concentrated concentrate to obtain a secondary concentrated tailing and a bismuth grade of 25.25% and an operating recovery rate of 1. The flotation bismuth concentrate is subjected to weak magnetic separation to obtain a bismuth concentrate with a bismuth grade of 34.05% and an operating recovery rate of 95.63%, and a high-iron sulfur concentrate, wherein the magnetic field strength of the weak magnetic separation is 0.3 T; a collector and a frother are added to the flotation bismuth roughing tailings to perform a primary scavenging, to obtain a primary scavenging concentrate and a primary scavenging tailings; a collector and a frother are added to the primary scavenging tailings to perform a secondary scavenging, to obtain a secondary scavenging concentrate and a flotation bismuth tailings with a Sn grade of 0.79%, a WO3 grade of 1.10%, and a S grade of 9.75%;

[0050] S2. Sulfur flotation: Based on S1 pulp per ton, sulfuric acid 2000 g / ton, butyl xanthate 60 g / ton, and 2# oil 10 g / ton were added to the floating bismuth tailings obtained from S1 in sequence to perform a roughing operation to obtain a rougher concentrate and a floating sulfur rougher tailings; butyl xanthate 10 g / ton and 2# oil 5 g / ton were added to the rougher concentrate to perform a concentration operation to obtain a concentrated concentrate and a concentrated tailings; the concentrated concentrate was subjected to a secondary blank concentration operation to obtain a secondary concentrated tailings and a flotation pyrite with a sulfur grade of 44.63% and an operating recovery rate of 92.55%, and the flotation pyrite and the high-iron sulfur concentrate obtained from S1 were combined into a sulfur concentrate; butyl xanthate 15 g / ton and 2# oil 5 g / ton were added to the floating sulfur rougher tailings to perform a scavenging operation to obtain a scavenging concentrate and a floating sulfur tailing with a Sn grade of 0.93% and a WO3 grade of 1.28%;

[0051] S3. Tungsten flotation: adding a regulator, an activator, and a collector to the flotation sulfur tailings obtained in S2 in sequence to perform a roughing operation to obtain a roughing concentrate and a flotation tungsten roughing tailings; adding a regulator to the roughing concentrate to perform a concentration operation to obtain a concentration concentrate and a concentration tailings; performing a secondary blank concentration operation on the concentration concentrate to obtain a concentration tailings and a tungsten concentrate with a tungsten grade of 5.53% and an operating recovery rate of 92.66%; adding a collector to the flotation tungsten roughing tailings to perform a scavenging operation to obtain a scavenging concentrate and a flotation tungsten tailings with a Sn grade of 0.93%;

[0052] S4. Reselection of tin: The floating tungsten tailings obtained in S3 are sorted on a shaking table to obtain a tin concentrate with a Sn grade of 40.38% and an operating recovery rate of 36.55%, a tin secondary concentrate with a Sn grade of 4.36% and an operating recovery rate of 48.65%, and tailings.

[0053] The flow chart is as follows Figure 1 As shown in the figure, the grades of WO3, Sn, Bi and S in the final tailings were reduced to 0.05%, 0.20%, 0.02% and 0.60% respectively; the recoveries of WO3, Sn, Bi and S in the concentrate products were 84.81%, 76.50%, 83.81% and 90.90% respectively, indicating that the separation of tungsten, tin, bismuth and sulfur mixed concentrate by the method of the present invention can effectively realize the comprehensive recovery of the four valuable minerals.

[0054] Example 2 A method for separating tungsten, tin, bismuth and sulfur mixed concentrate

[0055] 1. Minerals

[0056] This embodiment takes a tungsten-tin mine in Yunnan as an example. After coarse grinding (-0.074mm accounts for less than 60%) and shaking table gravity separation, a tungsten-tin-bismuth-sulfur mixed concentrate with a Sn grade of 0.93%, a WO3 grade of 0.86%, a Bi grade of 1.36%, and an S grade of 18.99% is obtained.

[0057] 2. Separation Methods and Results

[0058] S1. Bismuth flotation: Grind the tungsten-tin-bismuth-sulfur mixed concentrate to -0.074mm, accounting for 87%, and then adjust the pulp to a concentration of 35% (w / v). Add the adjusting agent, collector, and frother to each ton of pulp according to the reagents and dosages in Table 1 to perform a roughing process to obtain a roughing concentrate and a roughing tailing with bismuth flotation. Add the adjusting agent and frother to the roughing concentrate to perform a concentration process to obtain a concentrated concentrate and a concentrated tailing. Perform a secondary blank concentration on the concentrated concentrate to obtain a secondary concentrated tailing and a bismuth grade of 19.84% and an operating recovery rate of 19.84%. 82.56% of the flotation bismuth concentrate, the flotation bismuth concentrate is subjected to weak magnetic separation to obtain a bismuth concentrate with a bismuth grade of 26.33% and an operating recovery rate of 93.26% and a high-iron sulfur concentrate, wherein the magnetic field strength of the weak magnetic separation is 0.45 T; a collector and a frother are added to the flotation bismuth roughing tailings to perform a primary scavenging, to obtain a primary scavenging concentrate and a primary scavenging tailings; a collector and a frother are added to the primary scavenging tailings to perform a secondary scavenging, to obtain a secondary scavenging concentrate and a flotation bismuth tailings with a Sn grade of 0.98%, a WO3 grade of 0.90%, and a S grade of 18.88%;

[0059] S2. Sulfur flotation: Based on S1 pulp per ton, sulfuric acid 3000 g / ton, butyl xanthate 90 g / ton, and 2# oil 10 g / ton were added to the floating bismuth tailings obtained from S1 in sequence to perform a roughing operation to obtain a rougher concentrate and a floating sulfur rougher tailings; butyl xanthate 10 g / ton and 2# oil 5 g / ton were added to the rougher concentrate to perform a concentration operation to obtain a concentrated concentrate and a concentrated tailings; the concentrated concentrate was subjected to a secondary blank concentration operation to obtain a secondary concentrated tailings and a flotation pyrite with a sulfur grade of 46.35% and an operating recovery rate of 92.65%, and the flotation pyrite and the high-iron sulfur concentrate obtained from S1 were combined into a sulfur concentrate; butyl xanthate 20 g / ton and 2# oil 10 g / ton were added to the floating sulfur rougher tailings to perform a scavenging operation to obtain a scavenging concentrate and a floating sulfur tailing with a Sn grade of 1.48% and a WO3 grade of 1.34%;

[0060] S3. Tungsten flotation: adding a regulator, an activator, and a collector to the flotation sulfur tailings obtained in S2 in sequence to perform a roughing operation to obtain a roughing concentrate and a flotation tungsten roughing tailings; adding a regulator to the roughing concentrate to perform a concentration operation to obtain a concentration concentrate and a concentration tailings; performing a secondary blank concentration operation on the concentration concentrate to obtain a concentration tailings and a tungsten concentrate with a tungsten grade of 6.22% and an operating recovery rate of 89.67%; adding a collector to the flotation tungsten roughing tailings to perform a scavenging operation to obtain a scavenging concentrate and a flotation tungsten tailings with a Sn grade of 1.81%;

[0061] S4. Reselection of tin: The floating tungsten tailings obtained in S3 are sorted on a shaking table to obtain tin concentrate with a Sn grade of 43.69% and an operating recovery rate of 46.88%, tin secondary concentrate with a Sn grade of 4.63% and an operating recovery rate of 42.65%, and tailings.

[0062] The grades of WO3, Sn, Bi and S in the final tailings were reduced to 0.08%, 0.22%, 0.07% and 1.49%, respectively; the recoveries of WO3, Sn, Bi and S in the concentrate products were 83.14%, 80.38%, 77.00% and 89.57%, respectively, indicating that the separation of tungsten, tin, bismuth and sulfur mixed concentrate by the method of the present invention can effectively achieve the comprehensive recovery of the four valuable minerals.

[0063] Example 3: A method for separating tungsten, tin, bismuth and sulfur mixed concentrate

[0064] 1. Minerals

[0065] This embodiment takes a tungsten-tin mine in Yunnan as an example. After coarse grinding (-0.074 mm accounts for less than 60%) and shaking table gravity separation, a tungsten-tin-bismuth-sulfur mixed concentrate with a Sn grade of 0.66%, a WO3 grade of 0.74%, a Bi grade of 1.87%, and an S grade of 21.44% is obtained.

[0066] 2. Separation Methods and Results

[0067] S1. Bismuth flotation: Grind the tungsten-tin-bismuth-sulfur mixed concentrate to -0.074mm, accounting for 90%, and then adjust the pulp to a concentration of 35% (w / v). Add a regulator, a collector, and a frother to each ton of pulp according to the reagents and dosages in Table 1 to perform a roughing operation to obtain a roughing concentrate and a roughing tailing with bismuth flotation. Add a regulator and a frother to the roughing concentrate to perform a concentration operation to obtain a concentrated concentrate and a concentrated tailing. Perform a secondary blank concentration on the concentrated concentrate to obtain a secondary concentrated tailing and a bismuth grade of 24.45% and an operating recovery rate of 24.45%. The flotation bismuth concentrate is subjected to weak magnetic separation to obtain a bismuth concentrate with a bismuth grade of 33.55% and an operating recovery rate of 91.09%, and a high-iron sulfur concentrate, wherein the magnetic field strength of the weak magnetic separation is 0.3 T; a collector and a frother are added to the flotation bismuth roughing tailings to perform a primary scavenging, to obtain a primary scavenging concentrate and a primary scavenging tailings; a collector and a frother are added to the primary scavenging tailings to perform a secondary scavenging, to obtain a secondary scavenging concentrate and a flotation bismuth tailings with a Sn grade of 0.70%, a WO3 grade of 0.78%, and a S grade of 22.53%;

[0068] S2. Sulfur flotation: Based on S1 slurry per ton, sulfuric acid 5000 g / ton, butyl xanthate 90 g / ton, and 2# oil 30 g / ton were added to the floating bismuth tailings obtained from S1 in sequence to perform a roughing operation to obtain a rougher concentrate and a floating sulfur rougher tailings; butyl xanthate 20 g / ton and 2# oil 10 g / ton were added to the rougher concentrate to perform a concentration operation to obtain a concentrated concentrate and a concentrated tailings; the concentrated concentrate was subjected to a secondary blank concentration operation to obtain a secondary concentrated tailings and a flotation pyrite with a sulfur grade of 45.63% and an operating recovery rate of 92.55%, and the flotation pyrite and the high-iron sulfur concentrate obtained from S1 were combined into a sulfur concentrate; butyl xanthate 15 g / ton and 2# oil 8 g / ton were added to the floating sulfur rougher tailings to perform a scavenging operation to obtain a scavenging concentrate and a floating sulfur tailing with a Sn grade of 1.21% and a WO3 grade of 1.33%;

[0069] S3. Tungsten flotation: adding a regulator, an activator, and a collector to the flotation sulfur tailings obtained in S2 in sequence to perform a roughing operation to obtain a roughing concentrate and a flotation tungsten roughing tailings; adding a regulator to the roughing concentrate to perform a concentration operation to obtain a concentration concentrate and a concentration tailings; then performing a secondary blank concentration operation on the concentration concentrate to obtain a concentration tailings and a tungsten concentrate with a tungsten grade of 6.87% and an operating recovery rate of 92.66%; adding a collector to the flotation tungsten roughing tailings to perform a scavenging operation to obtain a scavenging concentrate and a flotation tungsten tailings with a Sn grade of 1.42%;

[0070] S4. Reselection of tin: The floating tungsten tailings obtained in S3 are sorted on a shaking table to obtain tin concentrate with a Sn grade of 39.89% and an operating recovery rate of 60.88%, tin secondary concentrate with a Sn grade of 4.27% and an operating recovery rate of 28.55%, and tailings.

[0071] The grades of WO3, Sn, Bi and S in the final tailings were reduced to 0.05%, 0.15%, 0.08% and 1.87%, respectively; the recoveries of WO3, Sn, Bi and S in the concentrate products were 81.79%, 72.27%, 77.62% and 91.33%, respectively, indicating that the separation of tungsten, tin, bismuth and sulfur mixed concentrate by the method of the present invention can effectively achieve the comprehensive recovery of the four valuable minerals.

[0072] Table 1: Agents and dosages of S1 and S3 used in Examples 1 to 3 (g / ton S1 slurry)

[0073]

[0074]

[0075] The separation results of Examples 1 to 3 are summarized to obtain Table 2:

[0076] Table 2 Separation results of Examples 1 to 3

[0077]

[0078]

[0079] It can be seen that in the final concentrates obtained in Examples 1 to 3, the recovery rate of tungsten is as high as 81.79% to 84.81%, the recovery rate of tin is as high as 72.27% to 80.38%, the recovery rate of bismuth is as high as 77.00% to 83.81%, and the recovery rate of sulfur is as high as 89.57% to 91.33%, indicating that the method of the present invention can be used to separate the tungsten-tin-bismuth-sulfur mixed concentrate, and can effectively achieve the comprehensive recovery of the valuable elements tungsten, tin, bismuth and sulfur in the tungsten-tin-bismuth-sulfur mixed concentrate.

[0080] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for separating tungsten, tin, bismuth and sulfur mixed concentrate, characterized in that: The following steps are involved: S1. Bismuth flotation: After grinding and slurrying the tungsten-tin-bismuth-sulfur mixed concentrate, a regulator, a collector, and a frother are sequentially added to perform a roughing process to obtain a roughing concentrate and a bismuth flotation roughing tailing; a regulator and a frother are added to the roughing concentrate to perform a primary concentration process to obtain a primary concentrated concentrate and a primary concentrated tailing; the primary concentrated concentrate is subjected to a secondary blank concentration process to obtain a flotation bismuth concentrate and a secondary concentrated tailing, and the flotation bismuth concentrate is subjected to weak magnetic separation to obtain a bismuth concentrate and a high-iron sulfur concentrate; a collector and a frother are added to the bismuth flotation roughing tailing to perform a scavenging process to obtain a primary scavenging concentrate and a primary scavenging tailing; a collector and a frother are added to the primary scavenging tailing to perform a secondary scavenging process to obtain a secondary scavenging concentrate and a bismuth flotation tailing; S2. Sulfur flotation: Based on the tungsten, tin, bismuth and sulfur mixed concentrate after grinding and slurrying in S1 per ton, sulfuric acid 2000 to 5000 g / ton, butyl xanthate 60 to 100 g / ton, and 2# oil 10 to 30 g / ton were added to the floating bismuth tailings obtained in S1 in sequence to perform a roughing process to obtain a roughing concentrate and a floating sulfur roughing tailings; butyl xanthate 10 to 20 g / ton and 2# oil 5 to 10 g / ton were added to the roughing concentrate to obtain a concentrated concentrate and a concentrated tailings; a secondary blank concentration was performed on the primary concentrated concentrate to obtain flotation pyrite and a secondary concentrated tailings, and the flotation pyrite and the high-iron sulfur concentrate obtained in S1 were combined into a sulfur concentrate; butyl xanthate 15 to 20 g / ton and 2# oil 5 to 10 g / ton were added to the floating sulfur roughing tailings to perform a scavenging process to obtain a scavenging concentrate and a floating sulfur tailings; S3. Tungsten flotation: sequentially adding a regulator, an activator, and a collector to the flotation sulfur tailings obtained in S2 to perform a roughing operation to obtain a roughing concentrate and a flotation tungsten roughing tailings; adding a regulator to the roughing concentrate to perform a concentration operation to obtain a primary concentration concentrate and a primary concentration tailings; then performing a secondary blank concentration operation on the primary concentration concentrate to obtain a tungsten concentrate and a secondary concentration tailings; adding a collector to the flotation tungsten roughing tailings to perform a scavenging operation to obtain a primary scavenging concentrate and a flotation tungsten tailings; the activator in S3 is copper chloride; S4. Reselection of tin: The floating tungsten tailings obtained in S3 are sorted on a shaking table to obtain tin concentrate, tin sub-concentrate and tailings.

2. The separation method according to claim 1, characterized in that The adjusting agent in S1 is a mixture of lime and water glass.

3. The separation method according to claim 1, characterized in that The collector described in S1 is a mixture of butyl ammonium black medicine and Y89 yellow medicine.

4. The separation method according to claim 1, characterized in that The foaming agent in S1 is a mixture of terpene alcohol and polypropylene glycol alkyl ether, or a mixture of methyl amyl alcohol and polypropylene glycol alkyl ether.

5. The separation method according to claim 1, characterized in that The adjusting agent in S3 is a mixture of sodium silicate, sodium hexametaphosphate and aluminum sulfate.

6. The separation method according to claim 1, characterized in that S3 The collector is benzohydroxamic acid and C 7-9 A mixture of alkyl hydroxamic acids.

7. The separation method according to claim 1, characterized in that The specific process of flotation of bismuth in S1 is as follows: to each ton of tungsten-tin-bismuth-sulfur mixed concentrate after grinding and slurrying, 2000-4000 g of adjusting agent, 50-80 g of collecting agent and 20-30 g of frother are sequentially added to perform a roughing process to obtain a roughing concentrate and a flotation bismuth roughing tailing; to the roughing concentrate, 500-1000 g of adjusting agent and 10-20 g of frother are added to perform a concentrating process to obtain a concentrating concentrate and a concentrating tailing; and the first concentrating process is repeated. The selected concentrate is subjected to secondary blank selection to obtain flotation bismuth concentrate and secondary selected tailings. The flotation bismuth concentrate is subjected to weak magnetic separation to obtain bismuth concentrate and high iron sulfur concentrate. 10 to 30 grams of collector and 10 to 20 grams of frother are added to the flotation bismuth roughing tailings to perform a primary scavenging selection to obtain a primary scavenging concentrate and a primary scavenging tailings. 5 to 15 grams of collector and 5 to 10 grams of frother are added to the primary scavenging tailings to perform a secondary scavenging selection to obtain a secondary scavenging concentrate and flotation bismuth tailings.

8. The separation method according to claim 1, characterized in that The flotation tungsten described in S3 is calculated based on the tungsten, tin, bismuth and sulfur mixed concentrate after grinding and slurrying in S1 per ton. The specific process is: adding 400-800 g / ton of adjusting agent, 200-600 g / ton of activating agent and 400-800 g / ton of collector to the floating sulfur tailings obtained in S2 in sequence to perform a roughing selection to obtain a roughing concentrate and a floating tungsten roughing tailings; adding 200-600 g / ton of adjusting agent to the roughing concentrate to perform a concentration to obtain a concentrated concentrate and a concentrated tailings; then performing a secondary blank concentration on the concentrated concentrate to obtain a tungsten concentrate and a secondary concentrated tailings; adding 80-140 g / ton of collector to the floating tungsten roughing tailings to perform a scavenging selection to obtain a scavenging concentrate and a floating tungsten tailings.

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