A cassiterite collector and a beneficiation method of associated cassiterite lithium pegmatite

Abstract

The application provides a cassiterite collector and a beneficiation method of a lithium-bearing pegmatite containing associated cassiterite, and relates to the technical field of beneficiation. The cassiterite collector has good selectivity and weak collecting capacity for spodumene, and can pre-elute easily-float gangue minerals such as fluorite, calcite, apatite and hornblende, thereby reducing the difficulty of subsequent spodumene flotation and improving the quality of spodumene concentrate. The beneficiation method using the cassiterite collector enriches cassiterite before spodumene flotation, and simultaneously elutes easily-float gangue minerals such as fluorite, calcite, apatite and hornblende which affect the grade of spodumene concentrate. The cassiterite is purified by gravity separation to obtain cassiterite concentrate, and the recovery of cassiterite in pegmatite ore is realized. The impurities affecting the quality of spodumene concentrate are pre-eluted, the quality and recovery rate of spodumene concentrate are improved, and the economic benefit is greatly improved.

Description

Technical Field

[0001] This application relates to the field of mineral processing technology, and in particular to a cassiterite collector and a mineral processing method for associated lithium-bearing cassiterite pegmatite. Background Technology

[0002] Currently, coarse-grained cassiterite is generally recovered using gravity separation, while fine-grained cassiterite is mostly recovered using a combination of flotation and gravity separation. Flotation typically requires the addition of depressants such as water glass and sodium fluorosilicate, followed by the addition of cation activators such as lead nitrate. Then, anionic flotation with oleic acid, arsenoic acid, phosphonic acid, or hydroxamic acid is used to collect the cassiterite; alternatively, at lower pH values, collectors such as alkyl sulfonated succinic acid are used for flotation recovery of cassiterite.

[0003] Currently, there are two methods for recovering cassiterite from associated lithium-bearing pegmatites. One method is to recover it by gravity separation before spodumene flotation. This method requires a lot of gravity separation equipment, which has high investment costs and is not easy to manage. At the same time, a lot of washing water needs to be added during the gravity separation process, which affects the stability of subsequent spodumene flotation operations. The other method is to recover it by gravity separation in the spodumene flotation concentrate. Since a large amount of spodumene collector remains in the spodumene concentrate, the bridging effect of the collector causes spodumene and other minerals such as cassiterite to agglomerate. During the shaking table gravity separation process, it is easy to form agglomerates, which affects the recovery rate of cassiterite and the quality of the concentrate.

[0004] If traditional methods are used to recover cassiterite by flotation, cassiterite can only be recovered by flotation before spodumene flotation. However, the inhibitors, activators and collectors added during the conventional cassiterite flotation process all have varying degrees of impact on spodumene flotation.

[0005] In addition, lithium-bearing pegmatites often contain easily floatable gangue such as fluorite, calcite, apatite, and amphibole. Due to the addition of a large amount of collector during the flotation of spodumene, these easily floatable gangue are easily collected into the spodumene concentrate, thus affecting the quality of the spodumene concentrate. Summary of the Invention

[0006] The purpose of this application is to provide a cassiterite collector and a beneficiation method for associated cassiterite-bearing lithium pegmatite, aiming to solve the above-mentioned problems.

[0007] To achieve the above objectives, this application provides a cassiterite collector comprising a first component, a second component, a third component, a fourth component, and a fifth component;

[0008] The first component is sodium fatty acid, wherein the carbon chain length of the sodium fatty acid is 14-22; the second component is sodium petroleum sulfonate and / or sodium dodecylbenzene sulfonate; the third component is naphthenic acid; the fourth component is one or both of sodium polyoxyethylene ether sulfate and / or sodium dodecyl sulfate; and the fifth component is water.

[0009] In some embodiments, the cassiterite collector comprises, by weight percentage: 30% to 50% of a first component, 8% to 15% of a second component, 5% to 10% of a third component, 0.5% to 1% of a fourth component, and 20% to 40% of a fifth component.

[0010] This application also provides a beneficiation method for associated lithium-bearing cassiterite pegmatite, using the aforementioned cassiterite collector, comprising:

[0011] The lithium-bearing pegmatite ore containing cassiterite is ground to obtain a slurry with a pH value of 8-10;

[0012] The cassiterite collector is added to the slurry to carry out cassiterite flotation, resulting in cassiterite rough concentrate and cassiterite flotation tailings.

[0013] Sodium carbonate is added to the cassiterite rough concentrate to carry out cassiterite beneficiation, resulting in cassiterite beneficiation foam and cassiterite beneficiation tailings.

[0014] The cassiterite foam is subjected to gravity separation to obtain tin concentrate;

[0015] The cassiterite tailings were subjected to spodumene flotation to obtain spodumene concentrate.

[0016] In some embodiments, the cassiterite tailings are subjected to spodumene flotation, including:

[0017] The cassiterite flotation tailings are mixed with sodium hydroxide and sodium carbonate to form a slurry. Then, spodumene activator and spodumene collector are added and mixed before lithium roughing is carried out to obtain lithium flotation foam and lithium flotation underflow.

[0018] The lithium flotation foam and sodium carbonate are mixed and then subjected to three lithium refining processes to obtain spodumene concentrate and lithium refining tailings.

[0019] The lithium flotation underflow is mixed with spodumene activator and spodumene collector and then subjected to lithium scavenging 1-2 times to obtain scavenging foam and scavenging tailings.

[0020] In some embodiments, at least one of the following conditions is met:

[0021] a. The Sn content in the lithium-bearing pegmatite containing cassiterite is 0.02-0.3% by mass;

[0022] b. The grinding and screening process uses mineral particles with a particle size of less than or equal to 2 mm;

[0023] c. The fineness of the solid materials in the slurry is less than 0.074 mm, accounting for 50% to 80%;

[0024] d. The concentration of the slurry is 30-35%;

[0025] e. Sodium carbonate is added during the grinding process;

[0026] f. The amount of sodium carbonate used is 500-2000 g / t of raw ore.

[0027] In some embodiments, at least one of the following conditions is met:

[0028] a. The cassiterite collector is prepared as an aqueous solution with a mass fraction of 5-15%;

[0029] b. The dosage of the cassiterite collector is 100-800 g / t of raw ore;

[0030] c. The cassiterite flotation time is 3-5 minutes;

[0031] d. The amount of sodium carbonate used in each cassiterite beneficiation process is 100-500 g / t of raw ore;

[0032] e. The cassiterite is selected 1-2 times.

[0033] In some embodiments, the reselection includes spiral chute reselection and shaking table reselection, wherein the reselection includes:

[0034] The cassiterite foam is added to a spiral sluice for the first gravity separation to obtain spiral sluice concentrate and spiral sluice tailings.

[0035] The spiral chute concentrate is added to a shaking table for a second gravity separation to obtain the tin concentrate;

[0036] The second reselection includes:

[0037] The spiral chute concentrate is added to the first shaking table for first shaking table gravity separation to obtain first shaking table concentrate, first shaking table middlings and first shaking table tailings;

[0038] The tin concentrate is added to a second shaking table for second shaking table reseparation to obtain the tin concentrate.

[0039] In some embodiments, at least one of the following conditions is met:

[0040] a. The mixing time for the slurry preparation is 5-30 minutes, and the linear velocity of the impeller is 5.5-7.5 m / s;

[0041] b. In the lithium roughing step, the amount of sodium hydroxide used is 100-200 g / t of raw ore;

[0042] c. In the lithium roughing step, the amount of sodium carbonate used is 200-300 g / t of raw ore;

[0043] d. In the lithium roughing step, the amount of spodumene activator used is 100-400 g / t of raw ore;

[0044] e. The spodumene collector is one or more of oleic acid, sodium oleate, oxidized paraffin soap, naphthenic acid, and naphthenic acid soap;

[0045] f. The spodumene activator is one or both of calcium chloride and magnesium chloride;

[0046] g. The lithium coarse selection time is 3-5 minutes;

[0047] h. The amount of spodumene collector used in the lithium roughing step is 500-2000 g / t of raw ore.

[0048] In some embodiments, at least one of the following conditions is met:

[0049] a. In the first lithium beneficiation step, the amount of sodium carbonate used is 100-600 g / t of raw ore;

[0050] b. In the second lithium beneficiation step, the amount of sodium carbonate used is 100-400 g / t of raw ore;

[0051] c. In the third lithium beneficiation step, the amount of sodium carbonate used is 100-300g / t of raw ore.

[0052] In some embodiments, the lithium sweep is performed twice, satisfying at least one of the following conditions:

[0053] a. In the first lithium scavenging step, the amount of spodumene collector used is 100-500 g / t of raw ore;

[0054] b. In the second lithium scavenging step, the amount of spodumene collector used is 50-200 g / t of raw ore.

[0055] Compared with the prior art, the beneficial effects of this application include:

[0056] The cassiterite collector provided in this application has good selectivity but weak collecting ability for spodumene. It can pre-extract gangue minerals with good floatability, such as fluorite, calcite, apatite, and amphibole, reducing the difficulty of subsequent spodumene flotation and improving the quality of spodumene concentrate.

[0057] The beneficiation method for associated lithium-bearing cassiterite pegmatite provided in this application utilizes the cassiterite collector described herein. Cassiterite is enriched by flotation before spodumene flotation, while easily floatable gangue minerals such as fluorite, calcite, apatite, and amphibole, which affect the grade of spodumene concentrate, are simultaneously removed. Then, utilizing the density difference between cassiterite and other gangue minerals, gravity separation is used to purify the cassiterite, obtaining cassiterite concentrate, thus achieving the recovery of cassiterite from pegmatite-type ores. The beneficiation method for associated lithium-bearing cassiterite pegmatite of this application can recover cassiterite without an activator, while simultaneously removing impurities that affect the quality of spodumene concentrate in advance, improving the quality and recovery rate of spodumene concentrate, and significantly increasing economic benefits. The beneficiation method for associated lithium-bearing cassiterite pegmatite of this application also has the advantages of simple operation, stable process, low equipment investment, and convenient on-site production management. Attached Figure Description

[0058] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0059] Figure 1 This is a schematic flowchart of the beneficiation method for lithium-bearing pegmatite associated with cassiterite according to this application. Detailed Implementation

[0060] As used in this article:

[0061] "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0062] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0063] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0064] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0065] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0066] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0067] This application provides a cassiterite collector, comprising a first component, a second component, a third component, a fourth component, and a fifth component;

[0068] The first component is sodium fatty acid, wherein the carbon chain length of the sodium fatty acid is 14-22; the second component is sodium petroleum sulfonate and / or sodium dodecylbenzene sulfonate; the third component is naphthenic acid; the fourth component is one or both of sodium polyoxyethylene ether sulfate and / or sodium dodecyl sulfate; and the fifth component is water.

[0069] The first component can be one or more sodium fatty acids with a carbon chain length of 14, 15, 16, 17, 18, 19, 20, 21 or 22.

[0070] The cassiterite collector provided in this application can collect cassiterite without an activator when the pulp pH is 8-10. At the same time, it can collect most of the fluorite, calcite, apatite, amphibole, etc. It has a weak collecting ability for spodumene but good selectivity, which reduces the difficulty of subsequent spodumene flotation and improves the quality of spodumene concentrate.

[0071] In some embodiments, the cassiterite collector comprises, by weight percentage: 30% to 50% of a first component, 8% to 15% of a second component, 5% to 10% of a third component, 0.5% to 1% of a fourth component, and 20% to 40% of a fifth component.

[0072] The mass percentage of the first component can be, for example, any value between 30%, 35%, 40%, 45%, 50%, or 30% to 50%; the mass percentage of the second component can be, for example, any value between 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or 8% to 15%; the mass percentage of the third component can be, for example, any value between 5%, 6%, 7%, 8%, 9%, 10%, or 5% to 10%; the mass percentage of the fourth component can be, for example, any value between 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or 0.5% to 1%; and the mass percentage of the fifth component can be, for example, any value between 20%, 25%, 30%, 35%, 40%, or 20% to 40%.

[0073] This application also provides a beneficiation method for lithium-bearing pegmatites associated with cassiterite, using the aforementioned cassiterite collector. (See also...) Figure 1 ,include:

[0074] S100: A slurry obtained by grinding lithium-bearing pegmatite ore containing cassiterite, with a pH value of 8-10.

[0075] S200: Add cassiterite collector to slurry to carry out cassiterite flotation to obtain cassiterite rough concentrate and cassiterite flotation tailings;

[0076] S300: Add sodium carbonate to cassiterite rough concentrate to perform cassiterite beneficiation, and obtain cassiterite beneficiation foam and cassiterite beneficiation tailings;

[0077] S400: Re-separate the cassiterite foam to obtain tin concentrate;

[0078] S500: Spodumene flotation is performed on cassiterite tailings to obtain spodumene concentrate.

[0079] The beneficiation method for lithium-bearing pegmatite with associated cassiterite provided in this application uses the cassiterite collector of this application to enrich cassiterite by flotation before spodumene flotation. At the same time, easily floatable gangue minerals such as fluorite, calcite, apatite, and amphibole that affect the grade of spodumene concentrate are removed simultaneously. Then, taking advantage of the density difference between cassiterite and other gangue minerals, cassiterite is purified by gravity separation to obtain cassiterite concentrate, thus realizing the recovery of cassiterite from pegmatite-type ore.

[0080] The beneficiation method for associated lithium-bearing cassiterite in this application can recover cassiterite without an activator, while simultaneously removing impurities that affect the quality of spodumene concentrate, thus improving the quality and recovery rate of spodumene concentrate and significantly increasing economic benefits. The beneficiation method for associated lithium-bearing cassiterite in this application also has advantages such as simple operation, stable process, low equipment investment, and ease of on-site production management.

[0081] In step S100, the Sn content in the lithium-bearing pegmatite containing cassiterite is 0.02-0.3% by mass; after grinding, the ore particles with a diameter less than or equal to 2 mm are screened; sodium carbonate is added during the grinding process, and the amount of sodium carbonate used is 500-2000 g / t of raw ore, for example, it can be 500 g / t of raw ore, 600 g / t of raw ore, 700 g / t of raw ore, 800 g / t of raw ore, 900 g / t of raw ore, 1000 g / t of raw ore, 1200 g / t of raw ore, 1300 g / t of raw ore, 1500 g / t of raw ore, 1700 g / t of raw ore, 2000 g / t of raw ore or any value between 500 and 2000 g / t of raw ore.

[0082] The fineness of the solid material in the slurry obtained in step S100 is less than 0.074 mm, accounting for 50% to 80%. For example, it can be any value between 50%, 55%, 60%, 65%, 70%, 75%, 80%, or 50% to 80%, which is a mass percentage. The slurry concentration is 30-35%, for example, it can be any value between 30%, 31%, 32%, 33%, 34%, 35%, or 30-35%. The slurry concentration refers to the mass percentage of solid material in the slurry relative to the total mass of the slurry.

[0083] The cassiterite collector used in step S200 is prepared as an aqueous solution with a mass fraction of 5-15%, for example, it can be any value between 5%, 7%, 9%, 10%, 12%, 15% or 5-15%; the amount of cassiterite collector used is 100-800 g / t of raw ore, for example, it can be 100 g / t of raw ore, 200 g / t of raw ore, 300 g / t of raw ore, 400 g / t of raw ore, 500 g / t of raw ore, 600 g / t of raw ore, 700 g / t of raw ore or 800 g / t of raw ore; the cassiterite flotation time is 3-5 min.

[0084] In step S300, the cassiterite is refined 1-2 times, and the amount of sodium carbonate used each time is 100-500g / t of raw ore, for example, it can be 100g / t of raw ore, 200g / t of raw ore, 300g / t of raw ore, 400g / t of raw ore or 500g / t of raw ore.

[0085] The reselection process in step S400 includes spiral chute reselection and shaking table reselection, including:

[0086] The selected cassiterite foam was added to the spiral sluice for the first gravity separation, resulting in spiral sluice concentrate and spiral sluice tailings.

[0087] The spiral sluice concentrate is added to a shaking table for a second re-separation to obtain tin concentrate.

[0088] The second re-election includes:

[0089] The spiral chute concentrate is added to the first shaking table for first shaking table gravity separation to obtain the first shaking table concentrate, the first shaking table middlings and the first shaking table tailings;

[0090] The concentrate from the first shaking table is added to the second shaking table for reseparation to obtain tin concentrate.

[0091] In a preferred embodiment, step S500 involves subjecting the cassiterite flotation tailings to spodumene flotation, including:

[0092] The cassiterite flotation tailings are mixed with sodium hydroxide and sodium carbonate to form a slurry. Then, spodumene activator and spodumene collector are added and mixed before lithium roughing is carried out to obtain lithium flotation foam and lithium flotation underflow.

[0093] Lithium flotation foam and sodium carbonate are mixed and then subjected to three lithium refining processes to obtain spodumene concentrate and lithium refining tailings.

[0094] The lithium flotation underflow is mixed with spodumene activator and spodumene collector and then subjected to lithium scavenging 1-2 times to obtain scavenging froth and scavenging tailings.

[0095] In some embodiments, the stirring time for mixing and preparing the slurry is 5-30 minutes, and the linear velocity of the stirring impeller is 5.5-7.5 m / s.

[0096] In some embodiments, in the lithium roughing step, the amount of sodium hydroxide used is 100-200 g / t of raw ore; the amount of sodium carbonate used is 200-300 g / t of raw ore; and the amount of spodumene activator used is 100-400 g / t of raw ore.

[0097] In some embodiments, the spodumene collector is one or more of oleic acid, sodium oleate, oxidized paraffin soap, naphthenic acid, and naphthenic acid soap; the spodumene activator is one or two of calcium chloride and magnesium chloride.

[0098] In some embodiments, the lithium coarse selection time is 3-5 minutes.

[0099] In some embodiments, the amount of spodumene collector used in the lithium roughing step is 500-2000 g / t of raw ore.

[0100] In some embodiments, the amount of sodium carbonate used in the first lithium beneficiation step is 100-600 g / t of raw ore; the amount of sodium carbonate used in the second lithium beneficiation step is 100-400 g / t of raw ore; and the amount of sodium carbonate used in the third lithium beneficiation step is 100-300 g / t of raw ore.

[0101] In some embodiments, the lithium scavenging is performed twice. In the first lithium scavenging step, the amount of spodumene collector used is 100-500 g / t of raw ore; in the second lithium scavenging step, the amount of spodumene collector used is 50-200 g / t of raw ore.

[0102] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0103] Example 1

[0104] Example 1 first provides a novel cassiterite collector, comprising a first component sodium 18C oleate, a second component sodium dodecylbenzene sulfonate, a third component naphthenic acid, a fourth component sodium polyoxyethylene ether sulfate, and a fifth component water, which are prepared into a paste in a mass ratio of 48:9:10:0.5:32.5, and the novel cassiterite collector is prepared into an aqueous solution with a mass fraction of 5-15% for use.

[0105] Example 1 also provides a beneficiation method for lithium-bearing pegmatite associated with tin, wherein the raw lithium-bearing pegmatite ore, by mass percentage, contains: 0.08% Sn, 1.2% Li₂O, and 1.8% easily floatable gangue such as apatite and amphibole. The beneficiation method includes the following steps:

[0106] S1. Grind the lithium-bearing pegmatite ore containing associated tin to obtain a slurry with 60% of the solid material having a fineness of less than 0.074 mm. The slurry concentration is 33%, which is then used for cassiterite roughing.

[0107] S2. Cassiterite Flotation and Removal of Easily Floating Minerals: 200 g / ton of a novel cassiterite collector is added to the slurry obtained in S1 as a collector for cassiterite and easily floating gangue minerals. After thorough stirring, cassiterite and easily floating gangue minerals are floated to obtain cassiterite rough concentrate and cassiterite flotation tailings.

[0108] S3, Cassiterite rough concentrate beneficiation: Add 200 g / ton sodium carbonate from the raw ore to the flotation froth obtained in S2 and stir thoroughly; then carry out cassiterite beneficiation I, and the flotation froth enters beneficiation II operation, with the flotation underflow being incorporated into the tailings. In beneficiation II operation, add 100 g / ton sodium carbonate from the raw ore and stir thoroughly, then carry out cassiterite beneficiation II to obtain beneficiation II froth product, with the underflow of beneficiation II being returned to beneficiation I operation.

[0109] S4. The selected II foam obtained in S3 is fed into the spiral sluice gravity separation operation to obtain spiral sluice concentrate and spiral sluice tailings. The spiral sluice tailings are incorporated into the total tailings.

[0110] S5. Feed the spiral sluice concentrate described in step S4 into the shaking table gravity separation I operation to obtain shaking table I concentrate, shaking table I middlings and shaking table I tailings. The shaking table I middlings are returned to the spiral sluice gravity separation operation, and the shaking table I tailings are incorporated into the total tailings.

[0111] S6. Feed the concentrate from shaking table I described in step S5 into shaking table gravity separation II operation to obtain tin concentrate, middlings from shaking table II and tailings from shaking table II. The middlings from shaking table II are returned to shaking table gravity separation I operation, and the tailings from shaking table II are incorporated into the total tailings.

[0112] S7. Add sodium hydroxide and sodium carbonate as conditioning agents to the cassiterite flotation tailings described in step S2, stir to adjust the slurry, then add magnesium chloride as activator and stir, then add spodumene collector, stir and carry out lithium roughing, flotation time 3-5 minutes, flotation foam enters the cleaning operation, and flotation underflow enters the lithium scavenging operation.

[0113] S8, Lithium Refinement: Add sodium carbonate as a modifier to the flotation foam in S7 and perform lithium refinement three times to obtain spodumene concentrate. The refined tailings are returned to the previous operation in sequence.

[0114] S9. Lithium Scavenging: Add magnesium chloride activator to the flotation underflow obtained in S7, then add spodumene collector, stir, and perform lithium scavenging 1-2 times. The scavenging foam is returned to the previous operation in sequence, and the scavenging underflow is tailings.

[0115] The tin concentrate obtained in Example 1 contained 55.50% SnO2 with a tin recovery rate of 39.85%, and the spodumene concentrate contained 5.86% Li2O with a Li2O recovery rate of 87.58%. The contents of impurities P2O5 and Fe were 0.08% and 0.09%, respectively.

[0116] Example 2

[0117] The difference between Example 2 and Example 1 is that the lithium-bearing pegmatite ore with associated tin in Example 2 contains, by mass percentage: 0.03% SnO2, 1.03% Li2O, and 3.1% of easily floating gangue minerals (mainly fluorite and apatite).

[0118] Example 2 used the same experimental scheme as Example 1 to obtain tin concentrate containing 42.40% SnO2, lithium concentrate containing 5.43% Li2O, tin recovery rate of 35.34%, lithium recovery rate of 83.58%, and impurity contents of P2O5 and CaF2 in spodumene concentrate of 0.05% and 0.06%, respectively.

[0119] Example 3

[0120] The difference between Example 3 and Example 1 is that the lithium-bearing pegmatite ore associated with tin in Example 3, by mass percentage, contains 0.04% SnO2, 1.12% Li2O, and 2.9% easily floatable gangue minerals (mainly amphibole and apatite). The novel cassiterite collector in Example 3 comprises a first component of sodium 18C and 20C oleate, a second component of sodium petroleum sulfonate, a third component of naphthenic acid, a fourth component of sodium dodecyl sulfate, and a fifth component of water, prepared into a paste according to a mass ratio of 43:12:8:0.6:36.4. The novel cassiterite collector is also prepared as an aqueous solution with a mass fraction of 5-15% for use.

[0121] Example 3 uses the same experimental scheme as Example 1 to obtain tin concentrate containing 41.55% SnO2, lithium concentrate containing 5.36% Li2O, tin recovery rate of 36.54%, lithium recovery rate of 82.11%, and impurities P2O5 and Fe content of 0.08% and 0.18% respectively in spodumene concentrate.

[0122] Comparative Example 1

[0123] Comparative Example 1 provides a method for beneficiating lithium-bearing pegmatite with associated cassiterite. Compared to Example 1, the difference lies in that cassiterite is not pre-flotated; instead, spodumene flotation is performed directly. Cassiterite is recovered by gravity separation in the spodumene flotation concentrate, and the gravity separation process is the same as in Example 1. The spodumene flotation process is the same as in Example 1 and will not be described again.

[0124] The spodumene concentrate obtained in Comparative Example 1 contained 5.43% Li₂O with a Li₂O recovery rate of 85.44%, and the cassiterite concentrate had a grade of 55.98% and a tin recovery rate of 38.33%. The contents of impurities P₂O₅ and Fe were 0.18% and 0.21%, respectively.

[0125] The results of Example 1 show that the cassiterite concentrate recovery rate obtained using the scheme of this application is high, and the quality and recovery rate of spodumene concentrate are significantly improved.

[0126] Comparative Example 2

[0127] Comparative Example 2 provides a method for beneficiating lithium-bearing pegmatite with associated cassiterite. The difference from Example 2 is that cassiterite is not pre-flotated; instead, spodumene flotation is performed directly. Cassiterite is recovered by gravity separation in the spodumene flotation concentrate, and the gravity separation process is the same as in Example 1. The spodumene flotation process is the same as in Example 1 and will not be described again.

[0128] The tin concentrate obtained in Comparative Example 2 contained 42.68% SnO2, the lithium concentrate contained 5.04% Li2O, the tin recovery rate was 34.66%, the lithium recovery rate was 82.16%, and the contents of impurities P2O5 and CaF2 in the spodumene concentrate were 0.25% and 0.79%, respectively.

[0129] It is evident that by using the reagents and beneficiation methods provided in this application, a higher grade tin concentrate can be obtained compared to conventional methods, the lithium concentrate grade is 0.39 percentage points higher, and the recovery rate is 1.42 percentage points higher.

[0130] Comparative Example 3

[0131] Comparative Example 3 provides a method for beneficiating lithium-bearing pegmatite with associated cassiterite. The difference from Example 3 is that cassiterite is beneficiated using a conventional cassiterite flotation method followed by spodumene flotation. The cassiterite gravity separation process is similar to that of Example 3. The spodumene flotation process is the same as in Example 1 and will not be described again.

[0132] The tin concentrate obtained in Comparative Example 3 contained 36.55% SnO2, the lithium concentrate contained 4.58% Li2O, the tin recovery rate was 35.76%, the lithium recovery rate was 76.10%, and the contents of impurities P2O5 and Fe in the spodumene concentrate were 0.22% and 0.89%, respectively.

[0133] It is evident that by using the reagents and beneficiation methods provided in this application, a higher grade tin concentrate is obtained compared to conventional methods, the lithium concentrate grade is increased by 0.76 percentage points, and the recovery rate is increased by 6.01 percentage points.

[0134] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0135] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A beneficiation method for lithium-bearing pegmatite associated with cassiterite, characterized in that, The cassiterite collector, by mass percentage, comprises: a first component of 30% to 50%, a second component of 8% to 15%, a third component of 5% to 10%, a fourth component of 0.5% to 1%, and a fifth component of 20% to 40%. The first component is sodium fatty acid, wherein the carbon chain length of the sodium fatty acid is 14-22; the second component is sodium petroleum sulfonate and / or sodium dodecylbenzene sulfonate; the third component is naphthenic acid; the fourth component is one or both of sodium polyoxyethylene ether sulfate and / or sodium dodecyl sulfate; and the fifth component is water. The mineral processing method includes: The lithium-bearing pegmatite ore containing cassiterite is ground to obtain a slurry with a pH value of 8-10; The cassiterite collector is added to the slurry to carry out cassiterite flotation, resulting in cassiterite rough concentrate and cassiterite flotation tailings; Sodium carbonate is added to the cassiterite rough concentrate to carry out cassiterite beneficiation, resulting in cassiterite beneficiation foam and cassiterite beneficiation tailings. The cassiterite foam is subjected to gravity separation to obtain tin concentrate; The cassiterite tailings were subjected to spodumene flotation to obtain spodumene concentrate.

2. The beneficiation method for associated lithium-bearing cassiterite pegmatite according to claim 1, characterized in that, The flotation of the cassiterite tailings includes: The cassiterite flotation tailings are mixed with sodium hydroxide and sodium carbonate to form a slurry. Then, spodumene activator and spodumene collector are added and mixed before lithium roughing is carried out to obtain lithium flotation foam and lithium flotation underflow. The lithium flotation foam and sodium carbonate are mixed and then subjected to three lithium refining processes to obtain spodumene concentrate and lithium tailings. The lithium flotation underflow is mixed with spodumene activator and spodumene collector and then subjected to lithium scavenging 1-2 times to obtain scavenging foam and scavenging tailings.

3. The beneficiation method for associated lithium-bearing cassiterite pegmatite according to claim 1, characterized in that, At least one of the following conditions must be met: a. The Sn content in the lithium-bearing pegmatite containing cassiterite is 0.02-0.3% by mass; b. The grinding and screening process uses mineral particles with a particle size of less than or equal to 2 mm; c. The fineness of the solid materials in the slurry is less than 0.074 mm, accounting for 50% to 80%; d. The concentration of the slurry is 30-35%; e. Sodium carbonate is added during the grinding process; f. The amount of sodium carbonate used is 500-2000 g / t of raw ore.

4. The beneficiation method for associated lithium-bearing cassiterite pegmatite according to claim 1, characterized in that, At least one of the following conditions must be met: a. The cassiterite collector is prepared as an aqueous solution with a mass fraction of 5-15%; b. The dosage of the cassiterite collector is 100-800 g / t of raw ore; c. The cassiterite flotation time is 3-5 minutes; d. The amount of sodium carbonate used in each cassiterite beneficiation process is 100-500 g / t of raw ore; e. The cassiterite is selected 1-2 times.

5. The beneficiation method for associated lithium-bearing cassiterite pegmatite according to claim 1, characterized in that, The reselection includes spiral chute reselection and shaking table reselection, and the reselection includes: The cassiterite foam is added to a spiral sluice for the first gravity separation to obtain spiral sluice concentrate and spiral sluice tailings. The spiral chute concentrate is added to a shaking table for a second gravity separation to obtain the tin concentrate; The second reselection includes: The spiral chute concentrate is added to the first shaking table for first shaking table gravity separation to obtain first shaking table concentrate, first shaking table middlings and first shaking table tailings; The tin concentrate is added to a second shaking table for second shaking table reseparation to obtain the tin concentrate.

6. The beneficiation method for associated lithium-bearing cassiterite pegmatite according to claim 2, characterized in that, At least one of the following conditions must be met: a. The mixing time for the slurry preparation is 5-30 minutes, and the linear velocity of the impeller is 5.5-7.5 m / s; b. In the lithium roughing step, the amount of sodium hydroxide used is 100-200 g / t of raw ore; c. In the lithium roughing step, the amount of sodium carbonate used is 200-300 g / t of raw ore; d. In the lithium roughing step, the amount of spodumene activator used is 100-400 g / t of raw ore; e. The spodumene collector is one or more of oleic acid, sodium oleate, oxidized paraffin soap, naphthenic acid, and naphthenic acid soap; f. The spodumene activator is one or both of calcium chloride and magnesium chloride; g. The lithium coarse selection time is 3-5 minutes; h. The amount of spodumene collector used in the lithium roughing step is 500-2000 g / t of raw ore.

7. The beneficiation method for associated lithium-bearing cassiterite pegmatite according to claim 2, characterized in that, At least one of the following conditions must be met: a. In the first lithium beneficiation step, the amount of sodium carbonate used is 100-600 g / t of raw ore; b. In the second lithium beneficiation step, the amount of sodium carbonate used is 100-400 g / t of raw ore; c. In the third lithium beneficiation step, the amount of sodium carbonate used is 100-300g / t of raw ore.

8. The beneficiation method for associated lithium-bearing cassiterite pegmatite according to claim 2, characterized in that, The lithium sweep is performed twice, satisfying at least one of the following conditions: a. In the first lithium scavenging step, the amount of spodumene collector used is 100-500 g / t of raw ore; b. In the second lithium scavenging step, the amount of spodumene collector used is 50-200 g / t of raw ore.

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