A method for hierarchical separation and recovery of lithium, tin and tungsten from lithium polymetallic ore

Abstract

The present invention discloses a classification and separation method for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ore, comprising the following steps: grinding and screening the lithium polymetallic ore raw material to obtain a +0.15 mm particle size product A, a -0.15 mm to +0.045 mm particle size product B, and a -0.045 mm particle size product C, and successively using Nelson gravity separation, roughing / cleaning by shaking table, and high-gradient magnetic separation to perform classification and separation on product B and product C to obtain tungsten concentrate and tin concentrate, and respectively performing flotation or slurry magnetic separation on the coarse-grained tailings and fine-grained tailings after classification and separation to obtain high-grade lithium concentrate. The method of the present invention has the advantages of being green and low-carbon, having high economic benefits, strong operability, good separation effect, etc., and can realize the comprehensive recovery of tungsten, tin, and lithium in lithium polymetallic ore, and has broad practical significance for realizing the rational utilization of lithium polymetallic ore, as well as improving the comprehensive utilization rate of low-grade lithium polymetallic ore resources and the added value of products.

Description

Technical Field

[0001] The present invention belongs to the field of beneficiation methods for lithium polymetallic ores, and relates to a classification separation method for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ores. Background Art

[0002] Lithium metal is a strategic metal for industrial development and has been widely used in fields such as batteries, ceramics, glass, nuclear industry, and optoelectronics. Among them, the battery industry has become the largest consumer field of lithium. The main sources of lithium metal resources are salt lake lithium ores and hard rock lithium ores. The lithium-containing ores are mainly spodumene and lepidolite, followed by petalite and amblygonite. Among them, lepidolite ore is an important source of lithium resources in mines. Lepidolite often occurs as an iron isomorph, making triphylite weakly magnetic. At the same time, lithium polymetallic ores sometimes contain associated low-grade wolframite, cassiterite and other rare metals, which are also important elements that need to be comprehensively recovered.

[0003] At present, to comprehensively recover target elements from lithium polymetallic ores, mainly based on the property differences between useful minerals and gangue, conventional gravity separation, magnetic separation, flotation or combined processes can achieve effective separation. For example, the Chinese patent document with the application number 201510380467.8 discloses a beneficiation process for effectively separating tantalum, tin and triphylite. The principle process of magnetic separation first and then gravity separation is adopted to separate lithium, tantalum and tin, then gravity separation is used to recover tantalum, and finally flotation is used to comprehensively recover lithium. However, this process still has the following defects: 1) This process is not conducive to the comprehensive recovery of fine-grained resources. Especially in the gravity separation operation, it will cause serious loss of fine-grained resources; 2) Adopting the process of magnetic separation first and then gravity separation is not conducive to the comprehensive recovery of tantalum elements, and the specific magnetization coefficient of tantalum is low, which easily leads to high mutual inclusion in tin concentrates; 3) When using the flotation process for lithium recovery, the -0.038mm particle size fraction is not effectively recovered. In addition, there is no relevant report on comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ores. Therefore, how to overcome the above defects and obtain a beneficiation process for comprehensively recovering triphylite and important elements such as tungsten and tin from lithium polymetallic ores with green and low-carbon, high economic benefits, strong operability, and good separation effect has broad practical significance for realizing the comprehensive recovery of tungsten, tin, and lithium in lithium polymetallic ores, as well as improving the comprehensive utilization rate of lithium polymetallic ore resources and the added value of products. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a classification separation method for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ores with green and low-carbon, high economic benefits, strong operability, and good separation effect.

[0005] To solve the above technical problem, the present invention adopts the following technical solutions.

[0006] A classification separation method for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ore, comprising the following steps:

[0007] S1. Grind the raw lithium polymetallic ore.

[0008] S2. Screen the material obtained after grinding using sieves with apertures of 0.045 mm and 0.15 mm to obtain Product A, Product B, and Product C; Product A is the +0.15 mm particle size grade; Product B is the -0.15 mm to +0.045 mm particle size grade; Product C is the -0.045 mm particle size grade.

[0009] The subsequent treatment of Product B includes:

[0010] (1.1) Conduct Knelson concentration on Product B to obtain Knelson concentration concentrate 1 and Knelson concentration tailings 1;

[0011] (1.2) Conduct rough shaking table separation on Knelson concentration concentrate 1 to obtain rough shaking table separation concentrate 1 and rough shaking table separation tailings 1;

[0012] (1.3) Conduct fine shaking table separation on rough shaking table separation concentrate 1 to obtain tungsten-tin mixed concentrate 1 and fine shaking table separation tailings 1;

[0013] (1.4) Conduct high-gradient magnetic separation on tungsten-tin mixed concentrate 1 to obtain tungsten concentrate 1 and tin concentrate 1.

[0014] The subsequent treatment of Knelson concentration tailings 1, rough shaking table separation tailings 1, and fine shaking table separation tailings 1 further includes:

[0015] (2.1) Collect Knelson concentration tailings 1, rough shaking table separation tailings 1, and fine shaking table separation tailings 1;

[0016] (2.2) Mix Knelson concentration tailings 1, rough shaking table separation tailings 1, and fine shaking table separation tailings to conduct rough high-gradient magnetic separation I to obtain rough high-gradient magnetic separation I concentrate and rough high-gradient magnetic separation I tailings;

[0017] (2.3) Conduct rough high-gradient magnetic separation II on the rough high-gradient magnetic separation I tailings to obtain rough high-gradient magnetic separation II concentrate and tailings 1;

[0018] (2.4) Mix the rough high-gradient magnetic separation I concentrate and the rough high-gradient magnetic separation II concentrate to conduct fine flotation to obtain lithium concentrate 1 and fine flotation tailings;

[0019] (2.5) Conduct scavenger flotation on the fine flotation tailings to obtain lithium concentrate 1 and scavenger flotation tailings.

[0020] The subsequent treatment of Product C includes:

[0021] (3.1) Perform Nelson re-selection on product C to obtain Nelson re-selection concentrate 2 and Nelson re-selection tailings 2;

[0022] (3.2) Conduct rough shaking table separation on Nelson re-selection concentrate 2 to obtain rough shaking table separation concentrate 2 and rough shaking table separation tailings 2;

[0023] (3.3) Conduct fine shaking table separation on rough shaking table separation concentrate 2 to obtain tungsten-tin mixed concentrate 2 and fine shaking table separation tailings 2;

[0024] (3.4) Perform high-gradient magnetic separation on tungsten-tin mixed concentrate 2 to obtain tungsten concentrate 2 and tin concentrate 2.

[0025] The subsequent treatment of the Nelson re-selection tailings 2, rough shaking table separation tailings 2, and fine shaking table separation tailings 2 further includes:

[0026] (4.1) Collect the Nelson re-selection tailings 2, rough shaking table separation tailings 2, and fine shaking table separation tailings 2;

[0027] (4.2) Mix the Nelson re-selection tailings 2, rough shaking table separation tailings 2, and fine shaking table separation tailings 2 and conduct rough pulp magnetic separation I to obtain rough pulp magnetic separation I concentrate and rough pulp magnetic separation I tailings;

[0028] (4.3) Conduct rough pulp magnetic separation II on the rough pulp magnetic separation I tailings to obtain rough pulp magnetic separation II concentrate and tailings 2;

[0029] (4.4) Mix the rough pulp magnetic separation I concentrate and rough pulp magnetic separation II concentrate and conduct fine pulp magnetic separation to obtain lithium concentrate 2 and fine pulp magnetic separation tailings.

[0030] In the above classification and separation method, further improved, in step (1.1), perform Nelson re-selection on product B using a Nelson re-selection machine; during the Nelson re-selection process, the gravity multiple is 100G, the feeding concentration is 30%, and the flushing water flow is 4.5 L / min.

[0031] In the above classification and separation method, further improved, in step (1.4), perform high-gradient magnetic separation on tungsten-tin mixed concentrate 1 using a high-gradient magnetic separator; during the high-gradient magnetic separation process, the magnetic field intensity is 1.1 T - 1.2 T, and the pulse frequency is 200 times / min - 250 times / min.

[0032] In the above classification and separation method, further improved, in step (2.2), perform rough high-gradient magnetic separation I on the mixed material of Nelson re-selection tailings 1, rough shaking table separation tailings 1, and fine shaking table separation tailings 1 using a high-gradient magnetic separator; during the rough high-gradient magnetic separation process, the magnetic field intensity is 1.75 T.

[0033] For the above-mentioned classification and separation method, in a further improvement, in step (2.3), a high-gradient magnetic separator is used to perform high-gradient magnetic separation II on the tailings of high-gradient magnetic separation roughing I; the magnetic field strength during the high-gradient magnetic separation roughing process is 1.75 T.

[0034] For the above-mentioned classification and separation method, in a further improvement, in step (2.4), a flotation machine is used to perform flotation concentration on the mixed material of the concentrate of high-gradient magnetic separation roughing I and the concentrate of high-gradient magnetic separation roughing II; flotation reagents are also added during the flotation concentration process; the flotation reagents include: sodium carbonate, sodium hexametaphosphate, dodecylamine, and oxidized paraffin soap; the dosage of sodium carbonate is 40 g - 45 g of sodium carbonate added per ton of the mixed material; the dosage of sodium hexametaphosphate is 10 g - 15 g of sodium hexametaphosphate added per ton of the mixed material; the dosage of dodecylamine is 10 g - 15 g of dodecylamine added per ton of the mixed material; the dosage of oxidized paraffin soap is 15 g - 20 g of oxidized paraffin soap added per ton of the mixed material.

[0035] For the above-mentioned classification and separation method, in a further improvement, in step (2.5), a flotation machine is used to perform flotation scavenging on the tailings of flotation concentration; flotation reagents are also added during the flotation scavenging process; the flotation reagents include: sodium carbonate, sodium hexametaphosphate, dodecylamine, and oxidized paraffin soap; the dosage of sodium carbonate is 20 g - 25 g of sodium carbonate added per ton of the tailings of flotation concentration; the dosage of sodium hexametaphosphate is 5 g - 10 g of sodium hexametaphosphate added per ton of the tailings of flotation concentration; the dosage of dodecylamine is 5 g - 10 g of dodecylamine added per ton of the tailings of flotation concentration; the dosage of oxidized paraffin soap is 5 g - 10 g of oxidized paraffin soap added per ton of the tailings of flotation concentration; the tailings of flotation scavenging are returned to step (2.2) for high-gradient magnetic separation roughing I.

[0036] For the above-mentioned classification and separation method, in a further improvement, in step (3.1), a Nelson concentrator is used to perform Nelson concentration on product C; the gravity multiple during the Nelson concentration process is 80G, the feed concentration is 25%, and the washing water flow is 3.5 L / min.

[0037] For the above-mentioned classification and separation method, in a further improvement, in step (3.4), a high-gradient magnetic separator is used to perform high-gradient magnetic separation on tungsten-tin mixed concentrate 2; the magnetic field strength during the high-gradient magnetic separation process is 1.1 T - 1.2 T, and the pulse frequency is 200 times / minute - 250 times / minute.

[0038] For the above-mentioned classification and separation method, in a further improvement, in step (4.2), a slurry magnetic separator is used to perform slurry magnetic separation roughing I on the mixed material of the tailings of Nelson concentration 2, the tailings of shaking table roughing 2, and the tailings of shaking table concentration 2; the magnetic field strength during the slurry magnetic separation roughing I process is 1.75 T, and the magnetic medium is a mesh magnetic medium.

[0039] For the above-mentioned classification and separation method, further improved, in step (4.3), a slurry magnetic separator is used to perform rough magnetic separation II on the tailings of rough magnetic separation I of the slurry; during the process of rough magnetic separation II of the slurry, the magnetic field strength is 1.75 T, and the magnetic medium is a mesh magnetic medium.

[0040] For the above-mentioned classification and separation method, further improved, in step (4.4), a slurry magnetic separator is used to perform fine magnetic separation on the concentrate of rough magnetic separation I of the slurry and the concentrate of rough magnetic separation II of the slurry; during the process of fine magnetic separation of the slurry, the magnetic field strength is 1.75 T, and the magnetic medium is a mesh magnetic medium; the tailings of the fine magnetic separation of the slurry are returned to step (4.2) for rough magnetic separation I of the slurry.

[0041] For the above-mentioned classification and separation method, further improved, in step S1, a grinding mill is used to grind the lithium polymetallic ore raw material until the grinding fineness is 60% - 65% of -0.074 mm.

[0042] For the above-mentioned classification and separation method, further improved, in step S1, the water addition amount during the grinding process is controlled so that the mass ratio of water to the lithium polymetallic ore is 2:3; the mass percentage content of Li2O in the lithium polymetallic ore is ≥ 0.3%, the mass percentage content of WO3 is ≥ 0.01%, and the mass percentage content of Sn is ≥ 0.002%.

[0043] For the above-mentioned classification and separation method, further improved, in step S2, product A is returned to step S1 for grinding.

[0044] Compared with the prior art, the advantages of the present invention are as follows:

[0045] In view of the defects existing in the existing ore dressing processes, such as serious loss of fine-grained resources, low grade of tin concentrate, and low comprehensive utilization rate of lithium resources, the present invention creatively proposes a classification and separation method for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ores. By utilizing the differences in the dissociation degree, specific gravity, and magnetism of the target minerals, the classification and separation technical idea of "coarse grinding - classification - gravity separation of coarse and fine particle sizes to recover tungsten and tin - strong magnetic separation of tungsten and tin - magnetic flotation combined recovery of lithium from the tailings of coarse particle size gravity separation - magnetic separation of the slurry of tailings of fine particle size gravity separation to recover lithium" is adopted, so that minerals of different particle sizes can be recovered to the maximum extent. Specifically: First, the lithium polymetallic ore is ground and classified to obtain material products with different coarse and fine particle sizes, and then the classification and separation of "Nielsen + shaking table gravity separation to recover tungsten and tin - strong magnetic separation of tungsten and tin" are respectively adopted to ensure the recovery effect of fine-grained tungsten and tin, avoid entrainment of fine particle sizes during the separation process of coarse particle sizes, reduce the mutual inclusion of elements between concentrates, and moreover, for both coarse and fine particle sizes, the combined gravity (Nielsen) and magnetic separation can be used to recover tungsten and tin. Among them, the gravity-magnetic principle process is suitable for the characteristics of the minerals themselves, with small yields of tungsten and tin, which can greatly reduce the investment cost, as well as reduce the loss of iron-lithium mica in other concentrates. At the same time, according to the appropriate concentrations of gravity and magnetic separation respectively, the gravity-magnetic combination can reduce industrial water compared with the magnetic-gravity combination, which is beneficial to reducing the investment and operating costs of concentration in the process, and has the advantages of being green, low-carbon, economically efficient, and highly practical. It is very suitable for the recovery of target minerals with large specific gravity in low-grade lithium polymetallic ores. In addition, according to the characteristics of magnetic separation recovery of lithium minerals in the coarse and fine particle sizes of the gravity separation tailings, the magnetic flotation combined process is used to obtain high-grade iron-lithium mica from the coarse particle size products, and the slurry magnetic separation process is used to improve the recovery rate of iron-lithium mica from the fine particle size products. It can be seen that the comprehensive recovery of different particle size products by different processes can not only reduce the risk of clogging of the slurry magnetic separator by coarse particle sizes, but also weaken the influence of fine particle size slime on the flotation operation, thus ensuring the efficient recovery of iron-lithium mica. The classification and separation method for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ores of the present invention can not only improve the grade and recovery rate of lithium concentrate, but also improve the grade and recovery rate of tungsten concentrate and tin concentrate, realize the comprehensive recovery of tungsten, tin, and lithium in lithium polymetallic ores, solve the problem of difficult recovery of fine-grained minerals, and has the advantages of being green, low-carbon, high economic efficiency, strong operability, and good separation effect. It has broad practical significance for realizing the rational utilization of lithium polymetallic ores, especially low-grade lithium polymetallic ores, and improving the comprehensive utilization rate and product added value of lithium polymetallic ore resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0047] Figure 1 Schematic diagram of the classification and separation process flow for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ores in Embodiment 1 of the present invention. Detailed implementation mode

[0048] The present invention will be further described below in conjunction with the accompanying drawings of the specification and specific preferred embodiments, but the protection scope of the present invention is not limited thereby. The materials and instruments used in the following embodiments are all commercially available.

[0049] In the embodiment of the present invention, the ore used is a certain lithium polymetallic ore in Hunan. The mass percentage content of Li2O in the raw ore is 0.33%, the mass percentage content of WO3 is 0.019%, and the mass percentage content of Sn is 0.046%. The main useful minerals in the ore are zinnwaldite, wolframite, and cassiterite, and the gangue minerals are quartz, feldspar, etc.

[0050] Example 1

[0051] A classification and separation method for comprehensively recovering lithium, tin, and tungsten from a lithium polymetallic ore, specifically for comprehensively recovering lithium concentrate, tungsten concentrate, and tin concentrate from a lithium polymetallic ore. The process flow chart of its classification and separation is as Figure 1 shown, including the following steps:

[0052] S1. Grind the raw material of the lithium polymetallic ore. Specifically, based on the dry weight of each ton of raw ore, water is added to the raw ore at a liquid-solid ratio of 2:3, that is, the grinding concentration is 60%. Grinding is carried out in a grinding mill until the grinding fineness reaches 60% passing through -0.074mm.

[0053] S2. Screen the material (mill discharge) obtained after grinding with sieves with apertures of 0.045mm and 0.15mm to obtain Product A, Product B, and Product C. Among them, Product A is the +0.15mm particle size grade, Product B is the -0.15mm to +0.045mm particle size grade, and Product C is the -0.045mm particle size grade. Among them, Product A is returned to Step S1 for grinding.

[0054] In Step S2, the subsequent treatment of the obtained Product B includes:

[0055] (1.1) Conduct Knelson concentration on Product B. Specifically, Product B (-0.15mm to +0.045mm particle size grade) is fed into a Knelson concentrator for Knelson concentration. During the Knelson concentration process, the gravity multiple is 100G, the feed concentration is 30%, and the washing water flow is 4.5L / min to obtain Knelson concentrate 1 and Knelson tailings 1.

[0056] (1.2) Conduct rough shaking table separation on the Knelson concentrate 1. Specifically, the Knelson concentrate 1 obtained in Step (1.1) is fed into a shaking table for rough shaking table separation to obtain rough shaking table concentrate 1 and rough shaking table tailings 1.

[0057] (1.3) The rough concentrate 1 of the shaking table is subjected to shaking table cleaning, specifically: the rough concentrate 1 of the shaking table obtained in step (1.2) is fed into the shaking table for shaking table cleaning to obtain tungsten-tin mixed concentrate 1 and shaking table cleaning tailings 1.

[0058] (1.4) The tungsten-tin mixed concentrate 1 is subjected to high-gradient magnetic separation, specifically: the tungsten-tin mixed concentrate 1 obtained in step (1.3) is fed into a high-gradient magnetic separator for high-gradient magnetic separation, where the magnetic field strength during the high-gradient magnetic separation process is 1.1 T and the pulse frequency is 200 times per minute, to obtain tungsten concentrate 1 and tin concentrate 1.

[0059] The subsequent treatment of the above-mentioned Nelson gravity separation tailings 1, shaking table roughing tailings 1 and shaking table cleaning tailings 1 also includes:

[0060] (2.1) Collect the Nelson gravity separation tailings 1, shaking table roughing tailings 1 and shaking table cleaning tailings 1.

[0061] (2.2) The Nelson gravity separation tailings 1, shaking table roughing tailings 1 and shaking table cleaning tailings 1 are mixed for high-gradient magnetic separation roughing, specifically: the Nelson gravity separation tailings 1 obtained in step (1.1), the shaking table roughing tailings 1 obtained in step (1.2) and the shaking table cleaning tailings 1 obtained in step (1.3) are combined, and the resulting mixed material is fed into a high-gradient magnetic separator for high-gradient magnetic separation roughing I, where the magnetic field strength during the high-gradient magnetic separation roughing process is 1.75 T, to obtain high-gradient magnetic separation roughing I concentrate and high-gradient magnetic separation roughing I tailings.

[0062] (2.3) The high-gradient magnetic separation roughing I tailings are subjected to high-gradient magnetic separation roughing II, specifically: the high-gradient magnetic separation roughing I tailings obtained in step (2.2) are fed into a high-gradient magnetic separator for high-gradient magnetic separation roughing II, where the magnetic field strength during the high-gradient magnetic separation roughing II process is 1.75 T, to obtain high-gradient magnetic separation roughing II concentrate and tailings 1.

[0063] (2.4) The high-gradient magnetic separation roughing I concentrate and high-gradient magnetic separation roughing II concentrate are mixed for flotation cleaning, specifically: the high-gradient magnetic separation roughing I concentrate obtained in step (2.2) and the high-gradient magnetic separation roughing II concentrate obtained in step (2.3) are combined, and the resulting mixed material is fed into a flotation machine for flotation cleaning, where flotation reagents are also added during the flotation cleaning process. The flotation reagents include: sodium carbonate, sodium hexametaphosphate, dodecylamine and oxidized paraffin soap. The dosage of sodium carbonate is 40 g of sodium carbonate added per ton of the mixed material, the dosage of sodium hexametaphosphate is 10 g of sodium hexametaphosphate added per ton of the mixed material, the dosage of dodecylamine is 10 g of dodecylamine added per ton of the mixed material, and the dosage of oxidized paraffin soap is 15 g of oxidized paraffin soap added per ton of the mixed material, to obtain lithium concentrate 1 (flotation cleaning lithium concentrate) and flotation cleaning tailings.

[0064] (2.5) Conduct rough scavenging flotation on the tailings of fine flotation, specifically: Feed the tailings of fine flotation obtained in step (2.4) into a flotation machine for rough scavenging flotation. During the rough scavenging flotation process, flotation reagents are also added. The flotation reagents include: sodium carbonate, sodium hexametaphosphate, dodecylamine, and oxidized paraffin soap. The dosage of sodium carbonate is 20 g of sodium carbonate added per ton of the tailings of fine flotation, the dosage of sodium hexametaphosphate is 5 g of sodium hexametaphosphate added per ton of the tailings of fine flotation, the dosage of dodecylamine is 5 g of dodecylamine added per ton of the tailings of fine flotation, and the dosage of oxidized paraffin soap is 5 g of oxidized paraffin soap added per ton of the tailings of fine flotation, obtaining lithium concentrate 1 (rough scavenging lithium concentrate by flotation) and tailings of rough scavenging flotation. In this step, the tailings of rough scavenging flotation are returned to step (2.2) for high-gradient magnetic separation roughing.

[0065] In step S2, the subsequent treatment of the obtained product C includes:

[0066] (3.1) Conduct Knelson concentration on product C, specifically: Feed product C (-0.045 mm particle size) into a Knelson concentrator for Knelson concentration. During the Knelson concentration process, the gravity multiple is 80G, the feed concentration is 25%, and the washing water flow is 3.5 L / min, obtaining Knelson concentration concentrate 2 and Knelson concentration tailings 2.

[0067] (3.2) Conduct rough tabling on Knelson concentration concentrate 2, specifically: Feed Knelson concentration concentrate 2 obtained in step (3.1) into a table for rough tabling, obtaining rough tabling concentrate 2 and rough tabling tailings 2.

[0068] (3.3) Conduct fine tabling on rough tabling concentrate 2, specifically: Feed rough tabling concentrate 2 obtained in step (3.2) into a table for fine tabling, obtaining tungsten-tin mixed concentrate 2 and fine tabling tailings 2.

[0069] (3.4) Conduct high-gradient magnetic separation on tungsten-tin mixed concentrate 2 to obtain tungsten concentrate 2 and tin concentrate 2.

[0070] The subsequent treatment of the above-mentioned Knelson concentration tailings 2, rough tabling tailings 2, and fine tabling tailings 2 also includes:

[0071] (4.1) Collect Knelson concentration tailings 2, rough tabling tailings 2, and fine tabling tailings 2.

[0072] (4.2) Mix the Nelson re-election tailings 2, the roughing tailings 2 of the shaking table, and the cleaning tailings 2 of the shaking table for rough magnetic separation I of the slurry. Specifically: Combine the Nelson re-election tailings 2 obtained in step (3.1), the roughing tailings 2 of the shaking table obtained in step (3.2), and the cleaning tailings 2 of the shaking table obtained in step (3.3). Feed the obtained mixed material into a slurry magnetic separator for rough magnetic separation of the slurry. During the rough magnetic separation of the slurry, the magnetic field intensity is 1.75 T, and the magnetic medium is a mesh magnetic medium, obtaining the concentrate of rough magnetic separation I of the slurry and the tailings of rough magnetic separation I of the slurry.

[0073] (4.3) Conduct rough magnetic separation II on the tailings of rough magnetic separation I of the slurry. Specifically: Feed the tailings of rough magnetic separation I of the slurry obtained in step (4.2) into a slurry magnetic separator for rough magnetic separation II of the slurry. During the rough magnetic separation II of the slurry, the magnetic field intensity is 1.75 T, and the magnetic medium is a mesh magnetic medium, obtaining the concentrate of rough magnetic separation II of the slurry and tailings 2.

[0074] (4.4) Mix the concentrate of rough magnetic separation I of the slurry and the concentrate of rough magnetic separation II of the slurry for fine magnetic separation of the slurry. Specifically: Combine the concentrate of rough magnetic separation I of the slurry obtained in step (4.2) and the concentrate of rough magnetic separation II of the slurry obtained in step (4.3). Feed the obtained mixed material into a slurry magnetic separator for fine magnetic separation of the slurry. During the fine magnetic separation of the slurry, the magnetic field intensity is 1.75 T, and the magnetic medium is a mesh magnetic medium, obtaining lithium concentrate 2 and the tailings of fine magnetic separation of the slurry. In this step, the tailings of fine magnetic separation of the slurry are returned to step (4.2) for rough magnetic separation I of the slurry.

[0075] S3. Combine tungsten concentrate 1 and tungsten concentrate 2 into tungsten concentrate, combine tin concentrate 1 and tin concentrate 2 into tin concentrate, combine lithium concentrate 1 and lithium concentrate 2 into lithium concentrate, and combine tailings 1 and tailings 2 into tailings.

[0076] According to the above process method, the lithium polymetallic ore (the average mass percentage content of Li2O in these raw ores is 0.33%, the average mass percentage content of WO3 is 0.019%, and the average mass percentage content of Sn is 0.047%) is recovered multiple times, and the average recovery results are shown in Table 1.

[0077] Example 2

[0078] A hierarchical separation method for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ore, specifically for comprehensively recovering lithium concentrate, tungsten concentrate, and tin concentrate from lithium polymetallic ore, including the following steps:

[0079] S1. Grind the lithium polymetallic ore raw material. Specifically: Based on each ton of dry weight of the raw ore, add water to the raw ore at a liquid-solid ratio of 2:3, that is, the grinding concentration is 60%, and conduct grinding in a grinding mill until the grinding fineness reaches 65% of -0.074 mm.

[0080] S2. Use sieves with apertures of 0.045 mm and 0.15 mm to screen the material (mill discharge) obtained after grinding, obtaining Product A, Product B, and Product C. Among them, Product A is the +0.15 mm particle size fraction, Product B is the -0.15 mm to +0.045 mm particle size fraction, and Product C is the -0.045 mm particle size fraction. Product A is returned to Step S1 for grinding.

[0081] In Step S2, the subsequent treatment of the obtained Product B includes:

[0082] (1.1) Conduct Knelson concentration on Product B. Specifically: Feed Product B (-0.15 mm to +0.045 mm particle size fraction) into a Knelson concentrator for Knelson concentration. During the Knelson concentration process, the gravity multiple is 100G, the feed concentration is 30%, and the flushing water flow is 4.5 L / min, obtaining Knelson concentrate 1 and Knelson tailings 1.

[0083] (1.2) Conduct rough tabling on Knelson concentrate 1. Specifically: Feed Knelson concentrate 1 obtained in Step (1.1) into a table for rough tabling, obtaining rough table concentrate 1 and rough table tailings 1.

[0084] (1.3) Conduct fine tabling on rough table concentrate 1. Specifically: Feed rough table concentrate 1 obtained in Step (1.2) into a table for fine tabling, obtaining tungsten-tin mixed concentrate 1 and fine table tailings 1.

[0085] (1.4) Conduct high-gradient magnetic separation on tungsten-tin mixed concentrate 1. Specifically: Feed tungsten-tin mixed concentrate 1 obtained in Step (1.3) into a high-gradient magnetic separator for high-gradient magnetic separation. During the high-gradient magnetic separation process, the magnetic field intensity is 1.2 T, and the pulse frequency is 250 times per minute, obtaining tungsten concentrate 1 and tin concentrate 1.

[0086] The subsequent treatment of the above-mentioned Knelson tailings 1, rough table tailings 1, and fine table tailings 1 also includes:

[0087] (2.1) Collect Knelson tailings 1, rough table tailings 1, and fine table tailings 1.

[0088] (2.2) Mix the Nelson reselected tailings 1, the roughing table tailings 1, and the cleaning table tailings 1 for rough high-gradient magnetic separation. Specifically: Combine the Nelson reselected tailings 1 obtained in step (1.1), the roughing table tailings 1 obtained in step (1.2), and the cleaning table tailings 1 obtained in step (1.3). Feed the resulting mixed material into a high-gradient magnetic separator for rough high-gradient magnetic separation I. During the rough high-gradient magnetic separation process, the magnetic field intensity is 1.75 T, obtaining the concentrate of rough high-gradient magnetic separation I and the tailings of rough high-gradient magnetic separation I.

[0089] (2.3) Conduct rough high-gradient magnetic separation II on the tailings of rough high-gradient magnetic separation I. Specifically: Feed the tailings of rough high-gradient magnetic separation I obtained in step (2.2) into a high-gradient magnetic separator for rough high-gradient magnetic separation II. During the rough high-gradient magnetic separation II process, the magnetic field intensity is 1.75 T, obtaining the concentrate of rough high-gradient magnetic separation II and tailings 1.

[0090] (2.4) Mix the concentrate of rough high-gradient magnetic separation I and the concentrate of rough high-gradient magnetic separation II for cleaning flotation. Specifically: Combine the concentrate of rough high-gradient magnetic separation I obtained in step (2.2) and the concentrate of rough high-gradient magnetic separation II obtained in step (2.3). Feed the resulting mixed material into a flotation machine for cleaning flotation. During the cleaning flotation process, flotation reagents are also added. The flotation reagents include: sodium carbonate, sodium hexametaphosphate, dodecylamine, and oxidized paraffin soap. The dosage of sodium carbonate is 45 g of sodium carbonate added per ton of the mixed material, the dosage of sodium hexametaphosphate is 15 g of sodium hexametaphosphate added per ton of the mixed material, the dosage of dodecylamine is 15 g of dodecylamine added per ton of the mixed material, and the dosage of oxidized paraffin soap is 20 g of oxidized paraffin soap added per ton of the mixed material, obtaining lithium concentrate 1 (cleaning flotation lithium concentrate) and cleaning flotation tailings.

[0091] (2.5) Conduct scavenging flotation on the cleaning flotation tailings. Specifically: Feed the cleaning flotation tailings obtained in step (2.4) into a flotation machine for scavenging flotation. During the scavenging flotation process, flotation reagents are also added. The flotation reagents include: sodium carbonate, sodium hexametaphosphate, dodecylamine, and oxidized paraffin soap. The dosage of sodium carbonate is 25 g of sodium carbonate added per ton of the cleaning flotation tailings, the dosage of sodium hexametaphosphate is 10 g of sodium hexametaphosphate added per ton of the cleaning flotation tailings, the dosage of dodecylamine is 10 g of dodecylamine added per ton of the cleaning flotation tailings, and the dosage of oxidized paraffin soap is 10 g of oxidized paraffin soap added per ton of the cleaning flotation tailings, obtaining lithium concentrate 1 (scavenging flotation lithium concentrate) and scavenging flotation tailings. In this step, the scavenging flotation tailings are returned to step (2.2) for rough high-gradient magnetic separation I.

[0092] In step S2, the subsequent treatment of the obtained product C includes:

[0093] (3.1) Conduct Nielsen re-election on product C, specifically: Feed product C (-0.045mm particle size fraction) into a Nielsen re-election machine for Nielsen re-election. During the Nielsen re-election process, the gravity multiple is 80G, the feeding concentration is 25%, and the flushing water flow is 3.5 L / min, obtaining Nielsen re-election concentrate 2 and Nielsen re-election tailings 2.

[0094] (3.2) Conduct rough tabling on Nielsen re-election concentrate 2, specifically: Feed Nielsen re-election concentrate 2 obtained in step (3.1) into a magnetic separation table for rough tabling, obtaining rough tabling concentrate 2 and rough tabling tailings 2.

[0095] (3.3) Conduct fine tabling on rough tabling concentrate 2, specifically: Feed rough tabling concentrate 2 obtained in step (3.2) into a magnetic separation table for fine tabling, obtaining tungsten-tin mixed concentrate 2 and fine tabling tailings 2.

[0096] (3.4) Conduct high-gradient magnetic separation on tungsten-tin mixed concentrate 2 to obtain tungsten concentrate 2 and tin concentrate 2.

[0097] The subsequent treatment of the above-mentioned Nielsen re-election tailings 2, rough tabling tailings 2, and fine tabling tailings 2 also includes:

[0098] (4.1) Collect Nielsen re-election tailings 2, rough tabling tailings 2, and fine tabling tailings 2.

[0099] (4.2) Mix Nielsen re-election tailings 2, rough tabling tailings 2, and fine tabling tailings 2 for pulp magnetic separation roughing, specifically: Combine Nielsen re-election tailings 2 obtained in step (3.1), rough tabling tailings 2 obtained in step (3.2), and fine tabling tailings 2 obtained in step (3.3). Feed the resulting mixed material into a pulp magnetic separator for pulp magnetic separation roughing I. During the pulp magnetic separation roughing process, the magnetic field intensity is 1.75T, and the magnetic medium is a mesh magnetic medium, obtaining pulp magnetic separation roughing I concentrate and pulp magnetic separation roughing I tailings.

[0100] (4.3) Conduct pulp magnetic separation roughing II on the pulp magnetic separation roughing I tailings, specifically: Feed the pulp magnetic separation roughing I tailings obtained in step (4.2) into a pulp magnetic separator for pulp magnetic separation roughing II. During the pulp magnetic separation roughing process, the magnetic field intensity is 1.75T, and the magnetic medium is a mesh magnetic medium, obtaining pulp magnetic separation roughing II concentrate and tailings 2.

[0101] (4.4) Mix the concentrate of the first rough magnetic separation of the slurry and the concentrate of the second rough magnetic separation of the slurry for the fine magnetic separation of the slurry. Specifically: Combine the concentrate of the first rough magnetic separation of the slurry obtained in step (4.2) and the concentrate of the second rough magnetic separation of the slurry obtained in step (4.3). Feed the obtained mixed material into a slurry magnetic separator for the fine magnetic separation of the slurry. During the fine magnetic separation of the slurry, the magnetic field intensity is 1.75 T, and the magnetic medium is a mesh magnetic medium, obtaining lithium concentrate 2 and the tailings of the fine magnetic separation of the slurry. In this step, the tailings of the fine magnetic separation of the slurry are returned to step (4.2) for the first rough magnetic separation of the slurry.

[0102] S3. Combine tungsten concentrate 1 and tungsten concentrate 2 into tungsten concentrate, combine tin concentrate 1 and tin concentrate 2 into tin concentrate, combine lithium concentrate 1 and lithium concentrate 2 into lithium concentrate, and combine tailings 1 and tailings 2 into tailings.

[0103] According to the above process method, the lithium polymetallic ore (the average mass percentage content of Li2O in these raw ores is 0.34%, the average mass percentage content of WO3 is 0.019%, and the average mass percentage content of Sn is 0.046%) is recycled multiple times, and the average recycling results are shown in Table 1.

[0104] As can be seen from Table 1, in Example 1, after being treated by the classification and separation method of the present invention, the grade of Li2O in the obtained lithium concentrate is increased to 1.97%, and the recovery rate of Li2O is 80.0%; the grade of WO3 in the tungsten concentrate is increased to 5.80%, and the recovery rate of WO3 is 74.19%; the grade of Sn in the tin concentrate is increased to 38.67%, and the recovery rate of Sn is 48.97%. At the same time, in Example 2, the grade of Li2O in the obtained lithium concentrate is increased to 1.97%, and the recovery rate of Li2O is 80.29%; the grade of WO3 in the tungsten concentrate is increased to 5.806.01%, and the recovery rate of WO3 is 74.85%; the grade of Sn in the tin concentrate is increased to 40.22%, and the recovery rate of Sn is 51.91%. It can be seen that the classification and separation method of the present invention can comprehensively recover lithium, tungsten, and tin from lithium polymetallic ore, and the content of mutually contained elements between lithium concentrate, tungsten concentrate, and tin concentrate is relatively low, which can effectively recover lithium, tungsten, and tin resources, and has broad practical significance for improving the comprehensive utilization rate of lithium polymetallic ore resources and the added value of products.

[0105] Table 1 Test results in Example 1 and Example 2

[0106]

[0107] As can be seen from the above results, the classification and separation method of the present invention utilizes the differences in the liberation degree, specific gravity, and magnetic properties of target minerals, and adopts the classification and separation technical idea of "coarse grinding - classification - gravity separation of coarse and fine particle sizes to recover tungsten and tin - strong magnetic separation of tungsten and tin - magnetic flotation combined with gravity separation of tailings of coarse particle sizes to recover lithium - magnetic separation of slurry of tailings of fine particle sizes to recover lithium", enabling the maximized recovery of minerals of different particle sizes. It can not only improve the grade and recovery rate of lithium concentrate, but also improve the grade and recovery rate of tungsten concentrate and tin concentrate, realizing the comprehensive recovery of tungsten, tin, and lithium in lithium polymetallic ore, solving the problem of difficult recovery of fine-grained minerals, and having the advantages of being green and low-carbon, high economic benefits, strong operability, and good separation effect. It has broad practical significance for realizing the rational utilization of lithium polymetallic ore, especially low-grade lithium polymetallic ore, and improving the comprehensive utilization rate of lithium polymetallic ore resources and the added value of products.

[0108] The above are only the preferred embodiments of the present invention and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make many possible changes and modifications to the technical solution of the present invention by using the methods and technical contents disclosed above, or modify it into equivalent embodiments with equivalent changes. Therefore, any simple modification, equivalent replacement, equivalent change, and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A hierarchical separation method for comprehensively recovering lithium, tin, and tungsten from lithium polymetallic ore, characterized in that, It includes the following steps: S1. Grind the lithium polymetallic ore raw material; S2. Screen the material obtained after grinding with sieves having pore sizes of 0.045 mm and 0.15 mm to obtain Product A, Product B, and Product C; Product A is the +0.15 mm particle size grade; Product B is the -0.15 mm to +0.045 mm particle size grade; Product C is the -0.045 mm particle size grade; The subsequent treatment of Product B includes: (1.1) Conduct Knelson concentration on Product B to obtain Knelson concentrate 1 and Knelson tailings 1; (1.2) Conduct rough tabling on Knelson concentrate 1 to obtain rough table concentrate 1 and rough table tailings 1; (1.3) Conduct fine tabling on rough table concentrate 1 to obtain tungsten-tin mixed concentrate 1 and fine table tailings 1; (1.4) Conduct high-gradient magnetic separation on tungsten-tin mixed concentrate 1 to obtain tungsten concentrate 1 and tin concentrate 1; The subsequent treatment of the Knelson tailings 1, rough table tailings 1, and fine table tailings 1 also includes: (2.1) Collect the Knelson tailings 1, rough table tailings 1, and fine table tailings 1; (2.2) Mix the Knelson tailings 1, rough table tailings 1, and fine table tailings 1 and conduct rough high-gradient magnetic separation I to obtain rough high-gradient magnetic separation I concentrate and rough high-gradient magnetic separation I tailings; (2.3) Conduct rough high-gradient magnetic separation II on the rough high-gradient magnetic separation I tailings to obtain rough high-gradient magnetic separation II concentrate and tailings 1; (2.4) Mix the rough high-gradient magnetic separation I concentrate and rough high-gradient magnetic separation II concentrate and conduct flotation cleaning to obtain lithium concentrate 1 and flotation cleaning tailings; (2.5) Conduct flotation scavenging on the flotation cleaning tailings to obtain lithium concentrate 1 and flotation scavenging tailings; The subsequent treatment of Product C includes: (3.1) Conduct Knelson concentration on Product C to obtain Knelson concentrate ​ ​ ​ ​ ​ ​ ​ ​ 2. The grading and sorting method according to claim 1, wherein, In step (1.1), a Nelson reseparator is used to perform Nelson reseparation on product B; during the Nelson reseparation process, the gravity multiple is 100G, the feeding concentration is 30%, and the flushing water flow is 4.5 L / min. In step (1.4), a high-gradient magnetic separator is used to perform high-gradient magnetic separation on tungsten-tin mixed concentrate 1; during the high-gradient magnetic separation process, the magnetic field strength is 1.1 T - 1.2 T, and the pulse frequency is 200 times / minute - 250 times / minute.

3. The grading and sorting method according to claim 2, characterized in that In step (2.2), a high-gradient magnetic separator is used to perform rough high-gradient magnetic separation I on the mixed material of Nelson reseparation tailings 1, roughing table tailings 1, and cleaning table tailings 1; during the rough high-gradient magnetic separation process, the magnetic field strength is 1.75 T. In step (2.3), a high-gradient magnetic separator is used to perform rough high-gradient magnetic separation II on the tailings of rough high-gradient magnetic separation I; during the rough high-gradient magnetic separation process, the magnetic field strength is 1.75 T. In step (2.4), a flotation machine is used to perform cleaning flotation on the mixed material of the concentrate of rough high-gradient magnetic separation I and the concentrate of rough high-gradient magnetic separation II. During the cleaning flotation process, flotation reagents are also added; the flotation reagents include: sodium carbonate, sodium hexametaphosphate, dodecylamine, and oxidized paraffin soap; the dosage of sodium carbonate is 40 g - 45 g of sodium carbonate added per ton of the mixed material; the dosage of sodium hexametaphosphate is 10 g - 15 g of sodium hexametaphosphate added per ton of the mixed material; the dosage of dodecylamine is 10 g - 15 g of dodecylamine added per ton of the mixed material; the dosage of oxidized paraffin soap is 15 g - 20 g of oxidized paraffin soap added per ton of the mixed material. In step (2.5), a flotation machine is used to perform scavenging flotation on the tailings of cleaning flotation; during the scavenging flotation process, flotation reagents are also added; the flotation reagents include: sodium carbonate, sodium hexametaphosphate, dodecylamine, and oxidized paraffin soap; the dosage of sodium carbonate is 20 g - 25 g of sodium carbonate added per ton of the tailings of cleaning flotation; the dosage of sodium hexametaphosphate is 5 g - 10 g of sodium hexametaphosphate added per ton of the tailings of cleaning flotation; the dosage of dodecylamine is 5 g - 10 g of dodecylamine added per ton of the tailings of cleaning flotation; the dosage of oxidized paraffin soap is 5 g - 10 g of oxidized paraffin soap added per ton of the tailings of cleaning flotation; the tailings of scavenging flotation are returned to step (2.2) for rough high-gradient magnetic separation I.

4. The grading and sorting method according to any one of claims 1 to 3, characterized in that, In step (3.1), a Nelson reseparator is used to perform Nelson reseparation on product C; during the Nelson reseparation process, the gravity multiple is 80G, the feeding concentration is 25%, and the flushing water flow is 3.5 L / min. In step (3.4), a high-gradient magnetic separator is used to perform high-gradient magnetic separation on tungsten-tin mixed concentrate 2; during the high-gradient magnetic separation process, the magnetic field strength is 1.1 T - 1.2 T, and the pulse frequency is 200 times / minute - 250 times / minute.

5. The grading and sorting method according to claim 4, wherein In step (4.2), a slurry magnetic separator is used to perform rough slurry magnetic separation I on the mixed material of Nelson reseparation tailings 2, roughing table tailings 2, and cleaning table tailings 2; during the rough slurry magnetic separation I process, the magnetic field strength is 1.75 T, and the magnetic medium is a mesh magnetic medium. In step (4.3), a slurry magnetic separator is used to conduct the second rough magnetic separation of the tailings from the first rough magnetic separation of the slurry; during the second rough magnetic separation of the slurry, the magnetic field intensity is 1.75 T, and the magnetic medium is a mesh magnetic medium; In step (4.4), a slurry magnetic separator is used to conduct the fine magnetic separation of the concentrate from the first rough magnetic separation of the slurry and the concentrate from the second rough magnetic separation of the slurry; during the fine magnetic separation of the slurry, the magnetic field intensity is 1.75 T, and the magnetic medium is a mesh magnetic medium; the tailings from the fine magnetic separation of the slurry are returned to step (4.2) for the first rough magnetic separation of the slurry.

6. The grading and sorting method according to any one of claims 1 to 3, characterized in that, In step S1, a grinding mill is used to grind the lithium polymetallic ore raw material until the grinding fineness reaches 60% - 65% passing through -0.074 mm.

7. The grading and sorting method according to claim 6, wherein In step S1, during the grinding process, the mass ratio of the water addition amount to the lithium polymetallic ore is controlled to be 2:3; the mass percentage content of Li2O in the lithium polymetallic ore ≥ 0.3%, the mass percentage content of WO3 ≥ 0.01%, and the mass percentage content of Sn ≥ 0.002%.

8. The grading and sorting method according to any one of claims 1 to 3, characterized in that, In step S2, product A is returned to step S1 for grinding.

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