Method for enriching lithium from low-grade lithium clay ores

Abstract

This application provides a method for enriching lithium from low-grade lithium clay ore. The method includes the following steps: obtaining low-grade lithium clay ore; crushing and roasting the low-grade lithium clay ore to obtain sinter; scrubbing the sinter to cause it to rub against itself; performing secondary screening on the scrubbed sinter to obtain a primary screening material with a particle size less than or equal to 0.83 mm and a secondary screening material with a particle size less than or equal to 0.015 mm; and performing flotation on the primary screening material to obtain flotated material, wherein the flotated material is combined with the secondary screening material to form lithium concentrate. This method for enriching lithium from low-grade lithium clay ore can efficiently develop and utilize lithium resources in low-grade lithium clay ore.

Description

Technical Field

[0001] This invention relates to the field of mineral processing technology, and in particular to a method for enriching lithium from low-grade lithium clay ore. Background Technology

[0002] Due to its excellent physicochemical properties, lithium is widely used in high-tech industries, especially in batteries, new energy vehicles, medicine and aerospace. It has extremely high strategic value and is known as the new energy metal of the 21st century, a metal that can promote the progress of the world.

[0003] my country is rich in lithium resources, ranking fifth in the world in terms of lithium reserves. However, most of these resources are located on the Qinghai-Tibet Plateau, where development conditions are harsh. 70% of these are brine-type lithium deposits, and the technology for developing and utilizing brine-type lithium resources is not yet mature, resulting in concentrates with high magnesium and lithium content. The remaining 30% are pegmatite-type deposits. However, with the continuous development and utilization of high-grade pegmatite spodumene and lepidolite, the overall grade of lithium ore is declining. These factors combined mean that my country needs to import large quantities of lithium resources from abroad. To address this issue, exploring and developing technologies to obtain lithium from new lithium mineral resources is crucial.

[0004] Clay-type lithium ores have relatively low lithium content due to their mineralization properties, and the lithium-bearing minerals are finely distributed, making their development and utilization difficult. At present, there are few reports on the development and utilization of this type of deposit. Exploring and developing new lithium resources, such as low-grade lithium clay ores, and developing new reagents and processes for lithium mining are very important for achieving efficient utilization of lithium resources and are also of great significance for solving my country's lithium self-sufficiency problem. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for efficiently developing and utilizing lithium resources in low-grade lithium clay ore by enriching lithium from low-grade lithium clay ore.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A method for enriching lithium from low-grade lithium clay ore includes the following steps:

[0008] Obtain low-grade lithium clay ore;

[0009] The low-grade lithium clay ore is crushed and roasted to obtain a sinter.

[0010] The sintered material is scrubbed to separate the clayey minerals with lower hardness and particle size from the gangue minerals with higher hardness in the sintered ore components.

[0011] The sintered material after scrubbing is subjected to a two-stage sieving process to obtain a primary sieve material with a particle size of less than or equal to 0.83 mm and a secondary sieve material with a particle size of less than or equal to 0.015 mm.

[0012] The primary screening material is subjected to flotation to obtain flotated material, wherein the flotated material is combined with the secondary screening material to form lithium concentrate.

[0013] In one embodiment, the crushing and roasting treatment of the low-grade lithium clay ore includes the following steps:

[0014] The low-grade lithium clay ore is crushed to a particle size of less than or equal to 20 mm.

[0015] The low-grade lithium clay ore after crushing is roasted.

[0016] In one embodiment, the roasting temperature for roasting the crushed low-grade lithium clay ore is 100°C to 400°C.

[0017] In one embodiment, the roasting time for roasting the crushed low-grade lithium clay ore is 30 min to 60 min.

[0018] In one embodiment, the sintered material is subjected to a scrubbing process, specifically by placing the sintered material in a dispersion medium and then stirring and scrubbing it.

[0019] In one embodiment, the solid content is 50% to 80% when the sinter is placed in the dispersion medium.

[0020] In one embodiment, the scrubbing intensity of the agitation scrubbing is 800 r / min to 1200 r / min.

[0021] In one embodiment, the scrubbing time of the agitation scrubbing is 7 min to 15 min.

[0022] In one embodiment, before the step of performing flotation on the primary screening material and after the step of performing secondary screening on the sintered material after scrubbing, the method for enriching lithium from low-grade lithium clay ore further includes the step of grinding the primary screening material.

[0023] In one embodiment, the D85 of the primary sieve after grinding is less than or equal to 0.074 mm.

[0024] In one embodiment, the flotation operation on the primary sieved material includes the following steps:

[0025] The primary sieve material is subjected to decalcification treatment;

[0026] The primary sieved material after desulfurization is subjected to further desulfurization treatment.

[0027] In one embodiment, before the step of desulfurizing the primary sieve material after desulfurization treatment and after the step of decalcifying the primary sieve material, the method for enriching lithium from low-grade lithium clay ore further includes the following steps:

[0028] The primary sieved material after decalcification is then broken up.

[0029] In one embodiment, the decalcification treatment of the primary sieve material specifically involves sequentially performing decalcification rough selection, decalcification fine selection, and two decalcification scavenging processes on the primary sieve material.

[0030] In one embodiment, Na2CO3 and NaOH are selected as modifiers in the decalcification roughing process.

[0031] In one embodiment, the Na2CO3 is prepared as a 5% solution for decalcification and roughing.

[0032] In one embodiment, during the decalcification coarse screening, 1000g to 4000g of Na2CO3 is used as a modifier per ton of the primary screening product.

[0033] In one embodiment, the NaOH is prepared as a 5% solution for decalcification and roughing.

[0034] In one embodiment, 500g to 2000g of NaOH is used as a modifier per ton of the primary sieved material.

[0035] In one embodiment, sodium polystyrene sulfonate is used as an inhibitor in the decalcification roughing and decalcification scavenging processes.

[0036] In one embodiment, the sodium polystyrene sulfonate has a molecular weight of 50,000 to 1,000,000.

[0037] In one embodiment, the sodium polystyrene sulfonate is prepared as a 5% solution for use in decalcification roughing and decalcification scavenging.

[0038] In one embodiment, 200g to 2000g of the sodium polystyrene sulfonate is used as an inhibitor per ton of the primary sieved material.

[0039] In one embodiment, a fatty acid collector is selected as the collector in the decalcification roughing, decalcification fine selection and decalcification scavenging.

[0040] In one embodiment, the fatty acid collector is sodium fatty acid.

[0041] In one embodiment, the fatty acid collector is at least one of sodium oleate, oxidized paraffin soap, and oleic acid.

[0042] In one embodiment, the fatty acid collector is configured as a 6% solution for use in decalcification roughing, decalcification cleaning, and decalcification scavenging.

[0043] In one embodiment, during the decalcification and roughing process, 200g to 2000g of the fatty acid collector is used as a collector per ton of the primary sieve material.

[0044] In one embodiment, during the decalcification and refining process, 200g to 2000g of fatty acid collector is used per ton of primary sieve material.

[0045] In one embodiment, during the decalcification process, 200g to 2000g of fatty acid collector is used per ton of primary sieve material.

[0046] In one embodiment, the desulfurization treatment of the primary sieve material after desulfurization treatment specifically involves performing desulfurization roughing and desulfurization scavenging sequentially on the primary sieve material after decalcification treatment.

[0047] In one embodiment, CaO is selected as a modifier in the desulfurization coarse selection.

[0048] In one embodiment, CaO is used directly for desulfurization roughing.

[0049] In one embodiment, in the desulfurization coarse screening, 500g to 1500g of the CaO is used as a modifier per ton of the primary screening material.

[0050] In one embodiment, sodium polystyrene sulfonate is used as an inhibitor in the desulfurization coarse selection and the desulfurization scavenging selection.

[0051] In one embodiment, the sodium polystyrene sulfonate has a molecular weight of 50,000 to 1,000,000.

[0052] In one embodiment, the sodium polystyrene sulfonate is prepared as a 5% solution for use in desulfurization roughing and desulfurization scavenging.

[0053] In one embodiment, during the desulfurization coarse screening, 200g to 2000g of the sodium polystyrene sulfonate is used as an inhibitor per ton of the primary screening material.

[0054] In one embodiment, during the desulfurization scavenging process, 200g to 2000g of the sodium polystyrene sulfonate is used as an inhibitor per ton of the primary sieve material.

[0055] In one embodiment, a mixture of dodecylamine and butyl xanthate is used as a collector in the desulfurization roughing and desulfurization scavenging processes.

[0056] In one embodiment, the mass ratio of dodecylamine to butyl xanthate in the mixture of dodecylamine and butyl xanthate is 1:1.

[0057] In one embodiment, the mixture of dodecylamine and butyl xanthate is prepared as a 1% solution for use in desulfurization roughing and desulfurization scavenging.

[0058] In one embodiment, during the desulfurization coarse screening, 200g to 800g of the mixture of dodecylamine and butyl xanthate is used as a collector per ton of the primary screening material.

[0059] In one embodiment, during the desulfurization scavenging process, 200g to 800g of the mixture of dodecylamine and butyl xanthate is used as a collector per ton of the primary sieve material.

[0060] Compared with the prior art, the present invention has at least the following advantages:

[0061] This invention discloses a method for enriching lithium from low-grade lithium clay ore. Using low-grade lithium clay ore, it effectively develops and utilizes a relatively abundant but low-value mineral resource, while also supplementing lithium resources and alleviating the lithium shortage to some extent. Specifically, before roasting, the low-grade lithium clay ore is crushed into smaller particles, which facilitates sufficient roasting at a lower temperature. This loosens the structure of the lithium-containing minerals in the ore and ensures the hardness of the gangue minerals such as quartz and pyrite particles. This effectively ensures the difference in physical properties between the gangue mineral particles and the lithium-containing minerals. Furthermore, this physical property is utilized by scrubbing the sinter. Through this physical scrubbing, the loosened lithium-containing minerals formed on the surface of the sinter particles are separated from the gangue mineral particles and enriched. In other words, through roasting... The mutual friction and washing of the sintered material allows the lithium-bearing minerals with lower hardness and finer particle size to be separated from the gangue minerals with higher hardness. After the washing process, the particles of the harder gangue minerals, such as quartz and pyrite, remain relatively large, while the loosely structured lithium-bearing minerals are washed and enriched from the surface of the gangue mineral particles. At this point, the washed sintered material undergoes secondary screening. The secondary screening material with a particle size of less than or equal to 0.015 mm is lithium concentrate, while the primary screening material with a particle size of less than or equal to 0.83 mm (actually, the screening material with a particle size of less than or equal to 0.83 mm and greater than 0.015 mm) is flotation ore. This initial enrichment of lithium resources has been achieved, greatly reducing the amount of flotation ore required, thereby reducing the workload and cost of flotation ore processing, and further ensuring the efficient enrichment of lithium-bearing minerals. Attached Figure Description

[0062] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0063] Figure 1 This is a flowchart of a method for enriching lithium from low-grade lithium clay ore according to an embodiment of the present invention.

[0064] Figure 2 for Figure 1 Another flowchart of a method for enriching lithium from low-grade lithium clay ore is shown. Detailed Implementation

[0065] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0066] It should be noted that when an element is referred to as being "fixed to" another element, it can be directly attached to the other element or there may be an intervening element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or there may be an intervening element. The terms "vertical," "horizontal," "left," "right," and similar expressions used herein are for illustrative purposes only and do not represent the only possible implementation.

[0067] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0068] Please refer to the following: Figure 1 and Figure 2 This application provides a method for enriching lithium from low-grade lithium clay ore. To better understand the method for enriching lithium from low-grade lithium clay ore, the following further explanation is provided:

[0069] One embodiment of the method for enriching lithium from low-grade lithium clay ore includes the following steps:

[0070] S100. Obtaining low-grade lithium clay ore. It is understandable that the insufficient supply of lithium resources has led to increased purchasing costs. To compensate for the deficiencies in the development and utilization of existing mineral resources and to increase the efficient development and utilization of lithium resources, low-grade lithium clay ore is used. This effectively develops and utilizes a large quantity of mineral resources with low value, while also replenishing lithium resources and alleviating the lithium shortage to some extent.

[0071] S200. Low-grade lithium clay ore is crushed and roasted to obtain sinter. Roasting the low-grade lithium clay ore makes its structure loose. Further crushing the ore into smaller particles before roasting allows for sufficient roasting at lower temperatures, resulting in a looser structure of lithium-containing minerals. This also ensures the hardness of gangue minerals such as quartz and pyrite particles, effectively differentiating the physical properties of gangue minerals from lithium-containing minerals. This facilitates the detachment and enrichment of lithium-containing minerals from the gangue mineral particles, leading to efficient enrichment of lithium-containing minerals in the low-grade lithium clay ore.

[0072] S300. The sintered material is scrubbed to allow the sintered material to rub against each other. It is understood that the gangue minerals such as quartz and pyrite particles in the sintered material formed after roasting crushed low-grade lithium clay ore have different physical properties from the lithium-bearing minerals. Specifically, the lithium-bearing minerals have a loose structure, while the gangue mineral particles retain a relatively high hardness. This physical property is further utilized by scrubbing the sintered material. Through this physical method, the loosely structured lithium-bearing minerals on the surface of the sintered material particles are separated and enriched from the gangue mineral particles. In other words, through the mutual friction and scrubbing of the sintered material, the lithium-bearing minerals with lower hardness and finer particle size in the sintered ore components are separated from the harder gangue minerals, effectively ensuring the efficient enrichment of lithium-bearing minerals.

[0073] S400. The sintered material after scrubbing is subjected to secondary sieving to obtain primary sieve material with a particle size of less than or equal to 0.83 mm and secondary sieve material with a particle size of less than or equal to 0.015 mm. It is understandable that after scrubbing, the harder gangue minerals such as quartz and pyrite still retain a relatively large particle size, while the loosely structured lithium-containing minerals are scrubbed and enriched from the surface of the gangue mineral particles. At this point, the scrubbed sinter is subjected to secondary screening. The secondary screening material with a particle size of less than or equal to 0.015 mm is lithium concentrate, while the primary screening material with a particle size of less than or equal to 0.83 mm (actually, the screening material with a particle size of less than or equal to 0.83 mm and greater than 0.015 mm) is flotation ore. At this point, the initial enrichment of lithium resources has been achieved, which greatly reduces the amount of flotation ore that needs to be flotated, thereby reducing the workload of flotation ore processing and reducing the processing cost of flotation ore, and further ensuring the efficient enrichment of lithium-containing minerals.

[0074] S500. The primary screening material is subjected to flotation to obtain flotated material, wherein the flotated material is combined with the secondary screening material to form lithium concentrate. It can be understood that after screening the scrubbed sinter, further flotation of the primary screening material, i.e., the raw flotation ore, effectively achieves sufficient enrichment of lithium in lithium-bearing minerals in low-grade lithium clay ore.

[0075] The aforementioned method for enriching lithium from low-grade lithium clay ore utilizes this ore, effectively developing and utilizing a relatively abundant but low-value mineral resource, while also supplementing lithium resources and alleviating the lithium shortage to some extent. Specifically, before roasting, the low-grade lithium clay ore is crushed into smaller particles, which facilitates sufficient roasting at lower temperatures. This loosens the structure of the lithium-bearing minerals in the ore and ensures the hardness of the gangue minerals such as quartz and pyrite particles. This effectively ensures the difference in physical properties between the gangue mineral particles and the lithium-bearing minerals. Furthermore, this physical property is utilized by scrubbing the sintered material. Through this physical scrubbing, the loosened lithium-bearing minerals on the surface of the sintered particles are separated from the gangue mineral particles and enriched. In other words, through sintering... The process involves mutual friction and washing of the materials to separate the lithium-bearing minerals with lower hardness and finer particle size from the gangue minerals with higher hardness in the sintered ore. After the washing process, the particles of the higher hardness gangue minerals, such as quartz and pyrite, remain relatively large, while the loosely structured lithium-bearing minerals are washed and enriched from the surface of the gangue mineral particles. At this point, the sintered material undergoes secondary screening. The secondary screening material with a particle size of less than or equal to 0.015 mm is lithium concentrate, while the primary screening material with a particle size of less than or equal to 0.83 mm (actually, the screening material with a particle size of less than or equal to 0.83 mm and greater than 0.015 mm) is flotation ore. This initial enrichment of lithium resources has been achieved, greatly reducing the amount of flotation ore required, thereby reducing the workload and cost of flotation ore processing, and further ensuring the efficient enrichment of lithium-bearing minerals.

[0076] It should be noted that the overall particle size of lithium-bearing minerals in roasted low-grade lithium clay ore is relatively fine, and they are easily broken and dispersed under external force. In contrast, gangue minerals such as quartz and pyrite have a coarser particle size and are not easily broken. Based on this difference in properties, this invention introduces a physical method of scrubbing to pre-scrub away the lithium clay minerals on the surface of the ore without affecting the useless gangue minerals such as quartz and pyrite on the surface of low-grade lithium clay ore, thereby achieving efficient initial enrichment of lithium.

[0077] It should also be noted that roasting is mainly used to enhance the scrubbing process. Roasting can loosen the structure of lithium-containing minerals in low-grade lithium clay ore, making the lithium-containing minerals easier to scrub off, reducing the amount of subsequent flotation processing, and thus reducing the cost of the flotation process.

[0078] In one embodiment, the crushing and roasting treatment of low-grade lithium clay ore includes the following steps: crushing the low-grade lithium clay ore to a particle size of 20 mm or less; further, crushing the low-grade lithium clay ore to a particle size completely ≤20 mm, i.e., the particle size of the crushed low-grade lithium clay ore is all below 20 mm. Further, the crushed low-grade lithium clay ore is roasted.

[0079] In one embodiment, the roasting temperature for roasting the crushed low-grade lithium clay ore is 100°C to 400°C, and the roasting time is 30 min to 60 min. It is understandable that high roasting temperatures significantly increase costs, and higher roasting temperatures also reduce the difference in physical properties between gangue minerals such as quartz and pyrite and lithium-bearing minerals. Therefore, the roasting temperature for low-grade lithium clay ore after crushing is 100℃ to 400℃. At this temperature, the lithium-bearing minerals can be effectively roasted and loosened, with minimal impact on the properties of the gangue minerals. This effectively reduces the cost of lithium enrichment from low-grade lithium clay ore while ensuring efficient and sufficient enrichment of lithium-bearing minerals during scrubbing. In addition to strengthening the scrubbing process, a certain amount of organic matter is often mixed into the ore during mining. Organic matter can affect the interaction between the ore and flotation reagents during flotation, deteriorating the flotation effect. However, under roasting temperatures of 100℃ to 400℃, organic matter can be effectively converted and removed, thus ensuring efficient and sufficient enrichment of lithium during flotation.

[0080] In one embodiment, the sinter is subjected to a scrubbing process, specifically by placing the sinter in a dispersion medium and then stirring and scrubbing it.

[0081] In one embodiment, the solid content of the sintered material is 50% to 80% when placed in a dispersion medium. Further, the dispersion medium is water.

[0082] In one embodiment, the scrubbing intensity of the agitation scrubbing is 800 r / min to 1200 r / min, and further, the scrubbing time is 7 min to 15 min.

[0083] In one embodiment, before the flotation operation on the primary screening material and after the secondary screening process on the scrubbed sinter, the method for enriching lithium from low-grade lithium clay ore further includes the step of grinding the primary screening material. Further, the D85 of the primary screening material after grinding is less than or equal to 0.074 mm, meaning the D85 of the primary screening material after grinding is below 0.074 mm. It can be understood that the D85 of the primary screening material represents the particle size of 85% of the primary screening material, and a D85 of less than 0.074 mm means that 85% of the primary screening material has a particle size below 0.074 mm, thus better ensuring the flotation effect of the primary screening material.

[0084] In one embodiment, the flotation operation on the primary sieved material includes the following steps:

[0085] The primary sieved material is subjected to decalcification treatment;

[0086] The primary sieved material after desulfurization is subjected to further desulfurization treatment.

[0087] In one embodiment, before the step of desulfurizing the primary screening material after desulfurization treatment and after the step of decalcifying the primary screening material, the method for enriching lithium from low-grade lithium clay ore further includes the step of dispersing the primary screening material after decalcification treatment.

[0088] In one embodiment, the primary sieve material is decalcified, specifically by sequentially performing decalcification roughing, decalcification fine selection, and two decalcification scavenging processes on the primary sieve material.

[0089] In one embodiment, Na₂CO₃ and NaOH are used as modifiers in the decalcification roughing process. Further, a 5% Na₂CO₃ solution is prepared for use in the decalcification roughing process. Even further, a 5% NaOH solution is prepared for use in the decalcification roughing process. Still further, the solvent for the solutions is water.

[0090] In one embodiment, during the decalcification coarse screening, 1000g to 4000g of Na2CO3 is used as a modifier per ton of primary screening material; further, 500g to 2000g of NaOH is used as a modifier per ton of primary screening material.

[0091] In one embodiment, sodium polystyrene sulfonate is used as an inhibitor in the decalcification roughing and decalcification scavenging processes. Further, the molecular weight of sodium polystyrene sulfonate is 50,000 to 1,000,000. Even further, the molecular weight of sodium polystyrene sulfonate is 200,000 or 600,000. Even further, sodium polystyrene sulfonate is prepared as a 5% solution for use in the decalcification roughing and decalcification scavenging processes. Even further, the solvent of the solution is water. It is understood that using sodium polystyrene sulfonate as an inhibitor results in a less pronounced inhibitory effect on gangue minerals such as pyrite, but improves selective inhibition, achieving a higher lithium enrichment ratio while ensuring lithium recovery.

[0092] In one embodiment, during the decalcification coarse screening, 200g to 2000g of sodium polystyrene sulfonate is used as an inhibitor per ton of primary screening material. Further, during the decalcification scavenging screening, 200g to 2000g of sodium polystyrene sulfonate is used as an inhibitor per ton of primary screening material.

[0093] In one embodiment, a fatty acid collector is selected as the collector in the decalcification roughing, decalcification cleaning, and decalcification scavenging processes. Further, the fatty acid collector is sodium fatty acid. Even further, the fatty acid collector is at least one selected from sodium oleate, oxidized paraffin soap, and oleic acid. Even further, the fatty acid collector is prepared as a 6% solution for use in the decalcification roughing, decalcification cleaning, and decalcification scavenging processes. Even further, the solvent of the solution is water.

[0094] In one embodiment, during the decalcification coarse selection, 200g to 2000g of fatty acid collector is used per ton of primary screening material. Further, during the decalcification fine selection, 200g to 2000g of fatty acid collector is used per ton of primary screening material. Even further, during the decalcification scavenging selection, 200g to 2000g of fatty acid collector is used per ton of primary screening material.

[0095] In one embodiment, the primary sieve material after desulfurization is subjected to desulfurization treatment, specifically by performing desulfurization rough selection and desulfurization scavenging on the primary sieve material after decalcification treatment in sequence.

[0096] In one embodiment, CaO is selected as a modifier in the desulfurization roughing process. Furthermore, CaO is used directly in the desulfurization roughing process.

[0097] In one embodiment, during the desulfurization coarse screening, 500g to 1500g of CaO is used as a modifier per ton of primary screening material.

[0098] In one embodiment, sodium polystyrene sulfonate is used as an inhibitor in the desulfurization roughing and desulfurization scavenging processes. Further, the molecular weight of sodium polystyrene sulfonate is 50,000 to 1,000,000. Even further, the molecular weight of sodium polystyrene sulfonate is 200,000 or 600,000. Even further, sodium polystyrene sulfonate is prepared as a 5% solution for use in the desulfurization roughing and desulfurization scavenging processes. Even further, the solvent of the solution is water.

[0099] In one embodiment, during the desulfurization coarse screening, 200g to 2000g of sodium polystyrene sulfonate is used as an inhibitor per ton of primary screening material. Further, during the desulfurization scavenging screening, 200g to 2000g of sodium polystyrene sulfonate is used as an inhibitor per ton of primary screening material.

[0100] In one embodiment, a mixture of dodecylamine and butyl xanthate is used as the collector in the desulfurization roughing and desulfurization scavenging processes. Further, the mass ratio of dodecylamine to butyl xanthate in the mixture is 1:1. Even further, the mixture of dodecylamine and butyl xanthate is prepared as a 1% solution for use in the desulfurization roughing and desulfurization scavenging processes.

[0101] In one embodiment, during the desulfurization coarse screening, a mixture of 200g to 800g of dodecylamine and butyl xanthate is used as a collector per ton of primary screened material. Further, during the desulfurization scavenging screening, a mixture of 200g to 800g of dodecylamine and butyl xanthate is used as a collector per ton of primary screened material.

[0102] It should be noted that butyl xanthate is also called alkyl xanthate, or alkyl dithiocarbonate; more specifically, butyl xanthate is C4H9OCSSNa. Furthermore, dodecylamine is CH3(CH2). 11 NH2.

[0103] It should also be noted that when sodium polystyrene sulfonate is used as an inhibitor of lithium-containing minerals, fatty acid collectors are used as collectors of calcium-containing minerals, and a mixture of dodecylamine and xanthate is used as a collector of silicon- and sulfur-containing minerals, the efficient separation of lithium-containing minerals and gangue minerals is achieved well when they are used in combination.

[0104] Compared with the prior art, the present invention has at least the following advantages:

[0105] This invention discloses a method for enriching lithium from low-grade lithium clay ore. Using low-grade lithium clay ore, it effectively develops and utilizes a relatively abundant but low-value mineral resource, while also supplementing lithium resources and alleviating the lithium shortage to some extent. Specifically, before roasting, the low-grade lithium clay ore is crushed into smaller particles, which facilitates sufficient roasting at a lower temperature. This loosens the structure of the lithium-containing minerals in the ore and ensures the hardness of the gangue minerals such as quartz and pyrite particles. This effectively ensures the difference in physical properties between the gangue mineral particles and the lithium-containing minerals. Furthermore, this physical property is utilized by scrubbing the sinter. Through this physical scrubbing, the loosened lithium-containing minerals formed on the surface of the sinter particles are separated from the gangue mineral particles and enriched. In other words, through roasting... The mutual friction and washing of the sintered material allows the lithium-bearing minerals with lower hardness and finer particle size to be separated from the gangue minerals with higher hardness. After the washing process, the particles of the harder gangue minerals, such as quartz and pyrite, remain relatively large, while the loosely structured lithium-bearing minerals are washed and enriched from the surface of the gangue mineral particles. At this point, the washed sintered material undergoes secondary screening. The secondary screening material with a particle size of less than or equal to 0.015 mm is lithium concentrate, while the primary screening material with a particle size of less than or equal to 0.83 mm (actually, the screening material with a particle size of less than or equal to 0.83 mm and greater than 0.015 mm) is flotation ore. This initial enrichment of lithium resources has been achieved, greatly reducing the amount of flotation ore required, thereby reducing the workload and cost of flotation ore processing, and further ensuring the efficient enrichment of lithium-bearing minerals.

[0106] The following are some specific embodiments. It should be noted that the following embodiments do not exhaust all possible situations, and the materials used in the following embodiments are commercially available unless otherwise specified.

[0107] Example 1

[0108] The mineral raw materials were taken from the No. 1 pit of a lithium clay mine in Guizhou Province. The Li content was 0.18%, the Ca content was 12.68%, the Si content was 24.89%, and the Fe content was 8.76%. Its phase analysis mainly showed that the minerals were lithium chlorite, quartz, calcite, and pyrite.

[0109] The method for enriching lithium from the No. 1 pit of a lithium clay mine includes the following steps:

[0110] Pretreatment: All large pieces of raw ore are crushed into materials with a maximum particle size of less than 20mm, and then roasted at 200℃ for 40min.

[0111] Scrubbing operation: Place the roasted material into the mixer cylinder, add water to adjust the solid content of the material to 60% during scrubbing, scrubbing intensity to 800 r / min, and scrubbing time to 7 min.

[0112] Coarse and fine classification: Using 0.83mm and 0.015mm sieves, the washed product is screened and classified. The oversize material larger than 0.83mm is directly discarded as tailings, the undersize material smaller than 0.015mm is directly used as lithium concentrate, and the oversize material between 0.83mm and 0.015mm is used as flotation raw ore.

[0113] Grinding operation: The flotation raw ore is ground to a fineness of 85% or more with a particle size of less than 0.074 mm.

[0114] Preparation of reagents: Prepare 5% solutions of sodium polystyrene sulfonate inhibitor, Na2CO3 and NaOH, 6% solution of sodium oleate, and 1% solution of a mixture of dodecylamine and butyl xanthate (mass ratio of dodecylamine to butyl xanthate is 1:1).

[0115] Flotation operation: A flotation process of first decalcification and then desulfurization is adopted. The decalcification flotation process is a "roughing, cleaning, and scavenging" process. The lithium product after decalcification enters the desulfurization process, which is a "roughing and scavenging" process. Specifically, Na2CO3 and NaOH are used as modifiers in the decalcification roughing process, with Na2CO3 dosage of 1000 g / t and NaOH dosage of 500 g / t. Sodium polystyrene sulfonate is added as an inhibitor in the decalcification roughing, decalcification scavenging, desulfurization roughing, and desulfurization scavenging processes, with a dosage of 200 g / t. Sodium oleate is added in the decalcification roughing, decalcification cleaning, and two decalcification scavenging processes, with a dosage of 200 g / t. CaO is added as a modifier in the desulfurization roughing process, with a dosage of 1200 g / t. Dodecylamine and butyl xanthate are added as collectors in the desulfurization roughing and desulfurization scavenging processes, with a dosage of 200 g / t.

[0116] Example 2

[0117] The mineral raw materials were taken from the No. 1 pit of a lithium clay mine in Guizhou Province. The Li content was 0.18%, the Ca content was 12.68%, the Si content was 24.89%, and the Fe content was 8.76%. Its phase analysis mainly showed that the minerals were lithium chlorite, quartz, calcite, and pyrite.

[0118] The method for enriching lithium from the No. 1 pit of a lithium clay mine includes the following steps:

[0119] Pretreatment: All large pieces of raw ore are crushed into materials with a maximum particle size of less than 20mm, and then roasted at 200℃ for 40min.

[0120] Scrubbing operation: The roasted material is placed into the agitator cylinder, and water is added to adjust the solid content of the material to 70% during scrubbing. The scrubbing intensity is 1000 r / min, and the scrubbing time is 12 min. Coarse and fine classification: Using 0.83 mm and 0.015 mm sieves, the scrubbed product is screened and classified. The oversize material larger than 0.83 mm is directly discarded as tailings, the undersize material smaller than 0.015 mm is directly used as lithium concentrate, and the oversize material between 0.83 mm and 0.015 mm is used as flotation ore.

[0121] Grinding operation: The flotation raw ore is ground to a fineness of 0.074 mm for particles of 85% or more.

[0122] Preparation of reagents: Prepare 5% solutions of sodium polystyrene sulfonate inhibitor, Na2CO3 and NaOH, 6% solution of sodium oleate, and 1% solution of a mixture of dodecylamine and butyl xanthate (mass ratio of dodecylamine to butyl xanthate is 1:1).

[0123] Flotation operation: A flotation process of first decalcification and then desulfurization is adopted. The decalcification flotation process is a "roughing, cleaning, and scavenging" process. The lithium product after decalcification enters the desulfurization process, which is a "roughing and scavenging" process. Specifically, Na2CO3 and NaOH are used as modifiers in the decalcification roughing process, with Na2CO3 dosage of 1000 g / t and NaOH dosage of 500 g / t. Sodium polystyrene sulfonate is added as an inhibitor in the decalcification roughing, decalcification scavenging, desulfurization roughing, and desulfurization scavenging processes, with a dosage of 200 g / t. Sodium oleate is added in the decalcification roughing, decalcification cleaning, and two decalcification scavenging processes, with a dosage of 200 g / t. CaO is added as a modifier in the desulfurization roughing process, with a dosage of 1200 g / t. Dodecylamine and butyl xanthate are added as collectors in the desulfurization roughing and desulfurization scavenging processes, with a dosage of 200 g / t.

[0124] Example 3

[0125] The mineral raw materials were taken from the No. 1 pit of a lithium clay mine in Guizhou Province. The Li content was 0.18%, the Ca content was 12.68%, the Si content was 24.89%, and the Fe content was 8.76%. Its phase analysis mainly showed that the minerals were lithium chlorite, quartz, calcite, and pyrite.

[0126] The method for enriching lithium from the No. 1 pit of a lithium clay mine includes the following steps:

[0127] Pretreatment: All large pieces of raw ore are crushed into materials with a maximum particle size of less than 20mm, and then roasted at 200℃ for 40min.

[0128] Scrubbing operation: Place the roasted material into the mixer cylinder, add water to adjust the solid content of the material to 80% during scrubbing, scrubbing intensity to 1200 r / min, and scrubbing time to 15 min.

[0129] Coarse and fine classification: Using 0.83mm and 0.015mm sieves, the washed product is screened and classified. The oversize material larger than 0.83mm is directly discarded as tailings, the undersize material smaller than 0.015mm is directly used as lithium concentrate, and the oversize material between 0.83mm and 0.015mm is used as flotation raw ore.

[0130] Grinding operation: The flotation raw ore is ground to a fineness of 0.074 mm for particles of 85% or more.

[0131] Preparation of reagents: Prepare 5% solutions of sodium polystyrene sulfonate inhibitor, Na2CO3 and NaOH, 6% solution of sodium oleate, and 1% solution of a mixture of dodecylamine and butyl xanthate (mass ratio of dodecylamine to butyl xanthate is 1:1).

[0132] Flotation operation: A flotation process of first decalcification and then desulfurization is adopted. The decalcification flotation process is a "roughing, cleaning, and scavenging" process. The lithium product after decalcification enters the desulfurization process, which is a "roughing and scavenging" process. Specifically, Na2CO3 and NaOH are used as modifiers in the decalcification roughing process, with Na2CO3 dosage of 1000 g / t and NaOH dosage of 500 g / t. Sodium polystyrene sulfonate is added as an inhibitor in the decalcification roughing, decalcification scavenging, desulfurization roughing, and desulfurization scavenging processes, with a dosage of 200 g / t. Sodium oleate is added in the decalcification roughing, decalcification cleaning, and two decalcification scavenging processes, with a dosage of 200 g / t. CaO is added as a modifier in the desulfurization roughing process, with a dosage of 1200 g / t. Dodecylamine and butyl xanthate are added as collectors in the desulfurization roughing and desulfurization scavenging processes, with a dosage of 200 g / t.

[0133] Example 4

[0134] The mineral raw materials were taken from the No. 2 mine of the lithium clay mine in Guizhou. The content of Li was 0.20%, Ca was 13.57%, Si was 26.11%, and Fe was 8.47%. Its phase analysis mainly showed that lithium chlorite, quartz, calcite and pyrite were the main components.

[0135] The method for enriching lithium from the No. 1 pit of a lithium clay mine includes the following steps:

[0136] Pretreatment: All large pieces of raw ore are crushed into materials with a maximum particle size of less than 20mm, and then roasted at 200℃ for 40min.

[0137] Scrubbing operation: Place the roasted material into the mixer cylinder, add water to adjust the solid content of the material to 70% during scrubbing, scrubbing intensity to 1000 r / min, and scrubbing time to 12 min.

[0138] Coarse and fine classification: Using 0.83mm and 0.015mm sieves, the washed product is screened and classified. The oversize material larger than 0.83mm is directly discarded as tailings, the undersize material smaller than 0.015mm is directly used as lithium concentrate, and the oversize material between 0.83mm and 0.015mm is used as flotation raw ore.

[0139] Grinding operation: The flotation raw ore is ground to a fineness of 0.074 mm for particles of 85% or more.

[0140] Preparation of reagents: Prepare 5% solutions of sodium polystyrene sulfonate inhibitor, Na2CO3 and NaOH, 6% solution of sodium oleate, and 1% solution of a mixture of dodecylamine and butyl xanthate (mass ratio of dodecylamine to butyl xanthate is 1:1).

[0141] Flotation operation: A flotation process of first decalcification and then desulfurization is adopted. The decalcification flotation process is a "roughing, cleaning, and scavenging" process. The lithium product after decalcification enters the desulfurization process, which is a "roughing and scavenging" process. Specifically, Na2CO3 and NaOH are used as modifiers in the decalcification roughing process, with Na2CO3 dosage of 1000 g / t and NaOH dosage of 500 g / t. Sodium polystyrene sulfonate is added as an inhibitor in the decalcification roughing, decalcification scavenging, desulfurization roughing, and desulfurization scavenging processes, with a dosage of 200 g / t. Sodium oleate is added in the decalcification roughing, decalcification cleaning, and two decalcification scavenging processes, with a dosage of 200 g / t. CaO is added as a modifier in the desulfurization roughing process, with a dosage of 1200 g / t. Dodecylamine and butyl xanthate are added as collectors in the desulfurization roughing and desulfurization scavenging processes, with a dosage of 200 g / t.

[0142] Example 5

[0143] The mineral raw materials were taken from the No. 2 mine of the lithium clay mine in Guizhou. The content of Li was 0.20%, Ca was 13.57%, Si was 26.11%, and Fe was 8.47%. Its phase analysis mainly showed that lithium chlorite, quartz, calcite and pyrite were the main components.

[0144] The method for enriching lithium from the No. 1 pit of a lithium clay mine includes the following steps:

[0145] Pretreatment: All large pieces of raw ore are crushed into materials with a maximum particle size of less than 20mm, and then roasted at 200℃ for 40min.

[0146] Scrubbing operation: Place the roasted material into the mixer cylinder, add water to adjust the solid content of the material to 70% during scrubbing, scrubbing intensity to 1000 r / min, and scrubbing time to 12 min.

[0147] Coarse and fine classification: Using 0.83mm and 0.015mm sieves, the washed product is screened and classified. The oversize material larger than 0.83mm is directly discarded as tailings, the undersize material smaller than 0.015mm is directly used as lithium concentrate, and the oversize material between 0.83mm and 0.015mm is used as flotation raw ore.

[0148] Grinding operation: The flotation raw ore is ground to a fineness of 0.074 mm for particles of 85% or more.

[0149] Preparation of reagents: Prepare 5% solutions of sodium polystyrene sulfonate inhibitor, Na2CO3 and NaOH, 6% solution of oxidized paraffin soap, and 1% solution of a mixture of dodecylamine and butyl xanthate (mass ratio of dodecylamine to butyl xanthate is 1:1).

[0150] Flotation operation: A flotation process of first decalcification and then desulfurization is adopted. The decalcification flotation process is a "roughing, cleaning, and scavenging" process. The lithium product after decalcification enters the desulfurization process, which is a "roughing and scavenging" process. Specifically, Na2CO3 and NaOH are used as modifiers in the decalcification roughing process, with Na2CO3 dosage of 2000 g / t and NaOH dosage of 800 g / t. Sodium polystyrene sulfonate is added as an inhibitor in the decalcification roughing, decalcification scavenging, desulfurization roughing, and desulfurization scavenging processes, with a dosage of 800 g / t. Oxygenated paraffin soap is added in the decalcification roughing, decalcification cleaning, and two decalcification scavenging processes, with a dosage of 800 g / t. CaO is added as a modifier in the desulfurization roughing process, with a dosage of 500 g / t. Dodecylamine and butyl xanthate are added as collectors in the desulfurization roughing and desulfurization scavenging processes, with a dosage of 400 g / t.

[0151] Example 6

[0152] The mineral raw materials were taken from the No. 2 mine of the lithium clay mine in Guizhou. The content of Li was 0.20%, Ca was 13.57%, Si was 26.11%, and Fe was 8.47%. Its phase analysis mainly showed that lithium chlorite, quartz, calcite and pyrite were the main components.

[0153] The method for enriching lithium from the No. 1 pit of a lithium clay mine includes the following steps:

[0154] Pretreatment: All large pieces of raw ore are crushed into materials with a maximum particle size of less than 20mm, and then roasted at 200℃ for 40min.

[0155] Scrubbing operation: Place the roasted material into the mixer cylinder, add water to adjust the solid content of the material to 70% during scrubbing, scrubbing intensity to 1000 r / min, and scrubbing time to 12 min.

[0156] Coarse and fine classification: Using 0.83mm and 0.015mm sieves, the washed product is screened and classified. The oversize material larger than 0.83mm is directly discarded as tailings, the undersize material smaller than 0.015mm is directly used as lithium concentrate, and the oversize material between 0.83mm and 0.015mm is used as flotation raw ore.

[0157] Grinding operation: The flotation raw ore is ground to a fineness of 0.074 mm for particles of 85% or more.

[0158] Preparation of reagents: Prepare 5% solutions of sodium polystyrene sulfonate inhibitor, Na2CO3 and NaOH, 6% solution of sodium oleate, and 1% solution of a mixture of dodecylamine and butyl xanthate (mass ratio of dodecylamine to butyl xanthate is 1:1).

[0159] Flotation operation: A flotation process of first decalcification and then desulfurization is adopted. The decalcification flotation process is a "roughing, cleaning, and scavenging" process. The lithium product after decalcification enters the desulfurization process, which is a "roughing and scavenging" process. Specifically, Na2CO3 and NaOH are used as modifiers in the decalcification roughing process, with Na2CO3 dosage of 2500 g / t and NaOH dosage of 1200 g / t. Sodium polystyrene sulfonate is added as an inhibitor in the decalcification roughing, decalcification cleaning, desulfurization roughing, and desulfurization scavenging processes, with a dosage of 1200 g / t. Sodium oleate is added in the decalcification roughing, decalcification cleaning, and two decalcification scavenging processes, with a dosage of 1200 g / t. CaO is added as a modifier in the desulfurization roughing process, with a dosage of 1000 g / t. Dodecylamine and butyl xanthate are added as collectors in the desulfurization roughing and desulfurization scavenging processes, with a dosage of 500 g / t.

[0160] Example 7

[0161] The mineral raw materials were taken from the No. 2 mine of the lithium clay mine in Guizhou. The content of Li was 0.20%, Ca was 13.57%, Si was 26.11%, and Fe was 8.47%. Its phase analysis mainly showed that lithium chlorite, quartz, calcite and pyrite were the main components.

[0162] The method for enriching lithium from the No. 1 pit of a lithium clay mine includes the following steps:

[0163] Pretreatment: All large pieces of raw ore are crushed into materials with a maximum particle size of less than 20mm, and then roasted at 200℃ for 40min.

[0164] Scrubbing operation: Place the roasted material into the mixer cylinder, add water to adjust the solid content of the material to 70% during scrubbing, scrubbing intensity to 1000 r / min, and scrubbing time to 12 min.

[0165] Coarse and fine classification: Using 0.83mm and 0.015mm sieves, the washed product is screened and classified. The oversize material larger than 0.83mm is directly discarded as tailings, the undersize material smaller than 0.015mm is directly used as lithium concentrate, and the oversize material between 0.83mm and 0.015mm is used as flotation raw ore.

[0166] Grinding operation: The flotation raw ore is ground to a fineness of 0.074 mm for particles of 85% or more.

[0167] Preparation of reagents: Prepare a 5% solution each of the inhibitor sodium polystyrene sulfonate, Na2CO3 and NaOH, a 6% solution of oleic acid, and a 1% solution of the mixture of dodecylamine and butyl xanthate (mass ratio of dodecylamine to butyl xanthate is 1:1).

[0168] Flotation operation: A flotation process of first decalcification and then desulfurization is adopted. The decalcification flotation process is a "roughing, cleaning, and scavenging" process. The lithium product after decalcification enters the desulfurization process, which is a "roughing and scavenging" process. Specifically, Na2CO3 and NaOH are used as modifiers in the decalcification roughing process, with Na2CO3 dosage of 4000 g / t and NaOH dosage of 2000 g / t. Sodium polystyrene sulfonate is added as an inhibitor in the decalcification roughing, decalcification cleaning, desulfurization roughing, and desulfurization scavenging processes, with a dosage of 2000 g / t. Oleic acid is added in the decalcification roughing, decalcification cleaning, and two decalcification scavenging processes, with a dosage of 1800 g / t. CaO is added as a modifier in the desulfurization roughing process, with a dosage of 1200 g / t. Dodecylamine and butyl xanthate are added as collectors in the desulfurization roughing and desulfurization scavenging processes, with a dosage of 800 g / t.

[0169] Example 8

[0170] The mineral raw materials were taken from the No. 2 mine of the lithium clay mine in Guizhou. The content of Li was 0.16%, Ca was 15.27%, Si was 27.12%, and Fe was 9.03%. Its phase analysis mainly showed lithium chlorite, quartz, calcite and pyrite.

[0171] The method for enriching lithium from the No. 1 pit of a lithium clay mine includes the following steps:

[0172] Pretreatment: All large pieces of raw ore are crushed into materials with a maximum particle size of less than 20mm, and then roasted at 200℃ for 40min.

[0173] Scrubbing operation: Place the roasted material into the mixer cylinder, add water to adjust the solid content of the material to 70% during scrubbing, scrubbing intensity to 1000 r / min, and scrubbing time to 12 min.

[0174] Coarse and fine classification: Using 0.83mm and 0.015mm sieves, the washed product is screened and classified. The oversize material larger than 0.83mm is directly discarded as tailings, the undersize material smaller than 0.015mm is directly used as lithium concentrate, and the oversize material between 0.83mm and 0.015mm is used as flotation raw ore.

[0175] Grinding operation: The flotation raw ore is ground to a fineness of 0.074 mm for particles of 85% or more.

[0176] Preparation of reagents: Prepare 5% solutions of sodium polystyrene sulfonate inhibitor, Na2CO3 and NaOH, 6% solution of sodium oleate, and 1% solution of a mixture of dodecylamine and butyl xanthate (mass ratio of dodecylamine to butyl xanthate is 1:1).

[0177] Flotation operation: A flotation process of first decalcification and then desulfurization is adopted. The decalcification flotation process is a "roughing, cleaning, and scavenging" process. The lithium product after decalcification enters the desulfurization process, which is a "roughing and scavenging" process. Specifically, Na2CO3 and NaOH are used as modifiers in the decalcification roughing process, with Na2CO3 dosage of 1000 g / t and NaOH dosage of 500 g / t. Sodium polystyrene sulfonate is added as an inhibitor in the decalcification roughing, decalcification scavenging, desulfurization roughing, and desulfurization scavenging processes, with a dosage of 200 g / t. Sodium oleate is added in the decalcification roughing, decalcification cleaning, and two decalcification scavenging processes, with a dosage of 200 g / t. CaO is added as a modifier in the desulfurization roughing process, with a dosage of 1200 g / t. Dodecylamine and butyl xanthate are added as collectors in the desulfurization roughing and desulfurization scavenging processes, with a dosage of 200 g / t.

[0178] Comparative Example 1

[0179] Compared with Example 2, water glass was added as an inhibitor in the decalcification roughing, decalcification scavenging, desulfurization roughing and desulfurization scavenging processes at a dosage of 1000 g / t. The remaining steps, mineral raw materials and reagent dosages were the same as in Example 2.

[0180] Comparative Example 2

[0181] Compared with Example 2, no washing operation was performed on the material after pretreatment, and the remaining steps, mineral raw materials and reagent dosages were the same as in Example 2.

[0182] Comparative Example 3

[0183] Compared with Example 2, the materials were not roasted in the pretreatment and were directly scrubbed. The remaining steps, mineral raw materials and reagent dosages were the same as in Example 2.

[0184] Comparative Example 4

[0185] Compared with Example 2, black powder was added as a collector during the desulfurization roughing and desulfurization scavenging processes, while the remaining steps, mineral raw materials and reagent dosages were the same as in Example 2.

[0186] The recoveries of lithium, calcium, silicon, and iron after treatment with lithium clay ore in Examples 1 to 8 and Comparative Examples 1 to 4 were measured respectively, and the results are shown in Table 1 below:

[0187] Table 1: Recovery rates of lithium, calcium, silicon, and iron

[0188]

[0189]

[0190] As shown in Table 1, when sodium polystyrene sulfonate was used as an inhibitor in combination with Na2CO3, NaOH, fatty acid collectors, CaO, dodecylamine, and butyl xanthate, the lithium recovery rates in Examples 1 to 8 were significantly higher than those obtained in Comparative Example 1 when water glass was used as an inhibitor. This indicates that the inhibitory effect of sodium polystyrene sulfonate combined with Na2CO3, NaOH, fatty acid collectors, CaO, dodecylamine, and butyl xanthate is significantly better than that of water glass. Furthermore, the lithium concentrate obtained from roasting, scrubbing, and flotation of lithium clay ore in Examples 1 to 8 showed higher grades and recovery rates compared to that obtained from flotation of lithium clay ore in Comparative Example 2. The grade and recovery rate of lithium concentrate obtained by direct flotation after roasting were improved. In Examples 1 to 8, the grade and recovery rate of lithium concentrate obtained by roasting lithium clay ore followed by scrubbing and then flotation were improved compared to those obtained in Comparative Example 3, where lithium clay ore was directly scrubbed and then flotation. This indicates that the combination of roasting and scrubbing operations resulted in more efficient development and utilization of lithium clay ore. In addition, the grades of silicon and iron in the lithium concentrate in Examples 1 to 8 were lower than those in Comparative Example 4, indicating that the mixed use of dodecylamine and butyl xanthate can better capture quartz and pyrite gangue in lithium ore than black xanthate.

[0191] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0192] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for enriching lithium from low-grade lithium clay ore, characterized in that, Includes the following steps: Obtain low-grade lithium clay ore; The low-grade lithium clay ore is crushed and roasted to obtain a sinter. The sintered material is scrubbed to cause the sintered material to rub against each other. The sintered material after scrubbing is subjected to a two-stage sieving process to obtain a primary sieve material with a particle size of less than or equal to 0.83 mm and a secondary sieve material with a particle size of less than or equal to 0.015 mm. The primary screening material is subjected to flotation to obtain flotated material, wherein the flotated material is combined with the secondary screening material to form lithium concentrate; The crushing and roasting process for the low-grade lithium clay ore includes the following steps: The low-grade lithium clay ore is subjected to crushing treatment to crush the low-grade lithium clay ore to a particle size of less than or equal to 20 mm; The low-grade lithium clay ore after crushing is then roasted. The roasting temperature for roasting the crushed low-grade lithium clay ore is 100℃~200℃. The flotation operation on the primary sieved material includes the following steps: The primary sieve material is subjected to decalcification treatment; The primary sieve material after decalcification is then subjected to desulfurization treatment; The primary sieved material is subjected to decalcification treatment, specifically by sequentially performing decalcification rough selection, decalcification fine selection, and two decalcification scavenging selections; wherein, Na2CO3 and NaOH are used as modifiers in the decalcification rough selection, sodium polystyrene sulfonate is used as inhibitor in the decalcification rough selection and the decalcification scavenging selection, and fatty acid collectors are used as collectors in the decalcification rough selection, the decalcification fine selection, and the decalcification scavenging selection; The primary sieve material after desulfurization treatment is subjected to desulfurization treatment, specifically by performing desulfurization roughing and desulfurization scavenging sequentially on the primary sieve material after two decalcification scavenging processes; wherein, CaO is used as a modifier in the desulfurization roughing process, sodium polystyrene sulfonate is used as an inhibitor in the desulfurization roughing process and the desulfurization scavenging process, and a mixture of dodecylamine and butyl xanthate is used as a collector in the desulfurization roughing process and the desulfurization scavenging process.

2. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The roasting time for the crushed low-grade lithium clay ore is 30 min to 60 min.

3. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The sintered material is subjected to a scrubbing treatment, specifically by placing the sintered material in a dispersion medium and then stirring and scrubbing it.

4. The method for enriching lithium from low-grade lithium clay ore according to claim 3, characterized in that, When the sintered material is placed in the dispersion medium, the solid content is 50% to 80%.

5. The method for enriching lithium from low-grade lithium clay ore according to claim 3, characterized in that, The scrubbing intensity of the stirring scrubbing is 800 r / min to 1200 r / min.

6. The method for enriching lithium from low-grade lithium clay ore according to claim 3, characterized in that, The scrubbing time for the stirring and scrubbing is 7 min to 15 min.

7. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, Before the step of performing flotation on the primary screening material and after the step of performing secondary screening on the sintered material after scrubbing, the method for enriching lithium from low-grade lithium clay ore further includes the step of grinding the primary screening material.

8. The method for enriching lithium from low-grade lithium clay ore according to claim 7, characterized in that, The D85 of the primary screened material after grinding is less than or equal to 0.074 mm.

9. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, Before and after the step of desulfurizing the primary sieve material after decalcification, the method for enriching lithium from low-grade lithium clay ore further includes the following steps: The primary sieved material after decalcification is then broken up.

10. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The Na2CO3 is prepared into a 5% solution for decalcification and roughing.

11. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the decalcification and roughing process, 1000g~4000g of Na2CO3 is used as a modifier per ton of the primary screening product.

12. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The NaOH is prepared into a 5% solution for decalcification and roughing.

13. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, 500g to 2000g of NaOH is used as a modifier per ton of the primary sieved material.

14. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The molecular weight of the sodium polystyrene sulfonate is 50,000 to 1,000,000.

15. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The sodium polystyrene sulfonate is prepared into a 5% solution for use in decalcification roughing and decalcification scavenging.

16. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, 200g to 2000g of sodium polystyrene sulfonate is used as an inhibitor per ton of the primary sieved material.

17. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The fatty acid collector is sodium fatty acid.

18. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The fatty acid collector is at least one of sodium oleate, oxidized paraffin soap, and oleic acid.

19. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The fatty acid collector is prepared as a 6% solution for use in decalcification roughing, decalcification cleaning, and decalcification scavenging.

20. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the decalcification and roughing process, 200g to 2000g of the fatty acid collector is used as a collector per ton of the primary screening material.

21. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the decalcification and beneficiation process, 200g to 2000g of fatty acid collectors are used per ton of primary screening material.

22. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the decalcification process, 200g to 2000g of fatty acid collectors are used per ton of primary screening material.

23. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, CaO is used directly in the desulfurization roughing process.

24. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the desulfurization coarse screening, 500g~1500g of CaO is used as a modifier per ton of the primary screening material.

25. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The molecular weight of the sodium polystyrene sulfonate is 50,000 to 1,000,000.

26. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The sodium polystyrene sulfonate is prepared into a 5% solution for use in desulfurization roughing and desulfurization scavenging.

27. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the desulfurization coarse screening, 200g~2000g of the sodium polystyrene sulfonate is used as an inhibitor per ton of the primary screening material.

28. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the desulfurization process, 200g to 2000g of sodium polystyrene sulfonate is used as an inhibitor per ton of the primary sieved material.

29. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The mass ratio of dodecylamine to butyl xanthate in the mixture is 1:

1.

30. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, The mixture of dodecylamine and butyl xanthate is prepared into a 1% solution for use in desulfurization roughing and desulfurization scavenging.

31. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the desulfurization roughing process, 200g to 800g of the mixture of dodecylamine and butyl xanthate is used as a collector per ton of the primary screening material.

32. The method for enriching lithium from low-grade lithium clay ore according to claim 1, characterized in that, In the desulfurization scavenging process, 200g to 800g of the mixture of dodecylamine and butyl xanthate is used as a collector per ton of the primary sieved material.

Images