Lithium mica collector and beneficiation method using lithium mica collector

Abstract

The application belongs to the technical field of mineral processing, and particularly relates to a lepidolite collector and a beneficiation method using the lepidolite collector. The lepidolite collector comprises 10-40 parts of sulfated rice bran oil acid, 10-40 parts of sodium dioctyl sulfonate, 10-30 parts of dodecylamine, 10-20 parts of isomeric decanol polyoxyethylene ether and 10-30 parts of calcium lignosulfonate in terms of weight. For high-mud and low-grade lepidolite ore, the method of the application can obtain high-grade lepidolite concentrate 1 and sub-high-grade lepidolite concentrate 2 at low temperature without pre-desliming, and the flotation froth is clean, non-sticky and easy to flow. Meanwhile, the lepidolite collector helps to improve the flotation recovery rate of lepidolite at low temperature (as low as 6 DEG C). The process flow is simple, the beneficiation index is good, the total Li2O recovery rate of the concentrate is greater than or equal to 85.0%, and the method has good popularization and application value.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of mineral processing, and particularly relates to a lepidolite collector and a beneficiation method using the lepidolite collector. BACKGROUND

[0002] Lithium mineral resources mainly come from salt lake brine and pegmatite ore. Due to the problems of difficult separation of lithium and magnesium, long production cycle and the like in the process of extracting lithium from salt lake brine, the extraction of lithium from brine cannot meet the market demand, and the extraction of lithium from ore occupies an important position. Lepidolite is one of the important raw materials for lithium extraction, and flotation is the most effective recovery method. With the year-by-year exploitation and utilization of lepidolite ore, the resource is becoming increasingly “poor, fine and impure”. When lepidolite ore is recovered under the commonly used strong acid amine flotation system (pH = 2-3) in industry, there are problems such as large consumption of sulfuric acid, difficulty in preparation of amine collectors, serious corrosion of equipment, sticky and difficult-to-break foaming in flotation, and difficulty in treatment and reuse of beneficiation wastewater.

[0003] In order to solve the above problems, existing researches mainly focus on the combination and application of anionic, cationic and non-ionic collectors. For example, the prior art CN115646660A provides a complex collector for lepidolite flotation based on the action of anions and cations and its application, which includes cations such as alkyl primary amine, ether amine with adjustable alkyl chain length, and anions such as C12-18 alkyl sodium sulfate, oleic acid, oxidized paraffin soap and amphoteric surfactant betaine; the prior art CN114160313A provides a lepidolite flotation collector and its application, which is a combination of anionic hydrocarbon sulfonate, sodium oleate and cationic alkyl polyamine ether, non-ionic polyoxyethylene sorbitol fatty acid ester and adjusting agent tannin; the prior art CN103240185A provides a new lepidolite flotation method, which uses anionic sodium oleate or oxidized paraffin soap and cationic dodecylamine or coconut amine for compounding. Compared with single cationic collector, the use of complex collector widens the optimal pH range of lepidolite high-efficiency selective flotation, and the flotation index is better. However, the anionic complex component, i.e. fatty acid collector, has poor solubility and dispersibility at low temperature (≤15℃), and the collecting capacity decreases sharply, which leads to a significant reduction in the recovery rate of lepidolite in winter and serious economic losses. Moreover, the collector has poor flowability at low temperature, and pipe blockage easily occurs. In addition, the existing complex collector has poor adaptability to low-grade high-mud lepidolite ore flotation, and cannot obtain high Li2O grade and Li2O recovery rate of concentrate products. SUMMARY

[0004] The present application aims to provide a lepidolite collector and a beneficiation method using the lepidolite collector, which has good effect on low-temperature flotation of low-grade high-mud lepidolite ore, can reduce the influence of high-content mud gangue on lepidolite flotation, and can adapt to fluctuations in ore properties to ensure high Li2O recovery rate.

[0005] To achieve the above object, the technical scheme adopted by the present application is:

[0006] A lithium mica collector, comprising 10-40 parts of sulfated rice bran oil acid, 10-40 parts of sodium dioctyl sulfosuccinate, 10-30 parts of dodecylamine, 10-20 parts of isomeric decanol polyoxyethylene ether and 10-30 parts of calcium lignosulfonate by weight.

[0007] In one preferred embodiment, the sulfated rice bran oil acid is obtained by sulfating rice bran oil acid, which comprises 35-45 parts of oleic acid, 35-40 parts of linoleic acid, 0.1-1.0 parts of linolenic acid, 15-20 parts of hexadecanoic acid and 1-2 parts of octadecanoic acid.

[0008] In one preferred embodiment, the preparation method of the sulfated rice bran oil acid comprises: adding sulfuric acid into rice bran oil acid in a stirring state in a molar ratio of 1:(0.8-1.2) in multiple times, adding saturated sodium sulfate aqueous solution after 1.5-2.5 hours of reaction to extract to obtain sulfated rice bran oil acid.

[0009] After the preparation of the sulfated rice bran oil acid (HOL), infrared spectroscopy, iodine value determination and liquid chromatography-mass spectrometry are used to verify the existence of the sulfated oil acid. The infrared spectroscopy test finds that the addition reaction of the unsaturated bond C=C in the rice bran oil acid occurs by comparing the infrared spectrograms of the rice bran oil acid and the sulfated rice bran oil acid, and the sulfuric acid group is introduced; the iodine value determination finds that the higher the proportion of the added concentrated sulfuric acid, the higher the proportion of the rice bran oil acid converted into the sulfated rice bran oil acid; the high performance liquid chromatography-mass spectrometry detects that there is an organic substance with a molecular weight of 380.16 in the modified rice bran oil acid, which is close to the molecular weight 380.5 of C 18 SO6H 36 , verifying the structure of the sulfated rice bran oil acid. The principle of the concentrated sulfuric acid modified rice bran oil acid is that compared with the rice bran oil acid molecule, the carbon-carbon double bond disappears in the sulfated rice bran oil acid, an ester sulfate group is introduced, and the carboxyl group still exists.

[0010] The molecular formula of the sodium dioctyl sulfosuccinate is C 20 H 38 NaO7S, and the structural formula is as follows:

[0011]

[0012] The molecular formula of the MOA is C 12 H 26 O2, and the structural formula is as follows:

[0013]

[0014] In one preferred embodiment, the lithium mica collector comprises sulfated rice bran oil acid 30 parts, sodium butanedioic acid diisooctyl ester sulfonate 30 parts, dodecylamine 20 parts, isomeric decanol polyoxyethylene ether 10 parts, calcium lignosulfonate 10 parts by weight;

[0015] In one preferred embodiment, the lithium mica collector comprises sulfated rice bran oil acid 28 parts, sodium butanedioic acid diisooctyl ester sulfonate 28 parts, dodecylamine 22 parts, isomeric decanol polyoxyethylene ether 11 parts, calcium lignosulfonate 11 parts by weight;

[0016] The present application also claims a beneficiation method using the lithium mica collector, comprising the following steps:

[0017] 1) Grinding: taking a proper amount of crushed raw ore for wet ball milling to obtain ore slurry I;

[0018] 2) Flotation: sequentially adding the combined depressant and the lithium mica collector to the ore slurry to perform a one-roughing-two-cleaning process, obtaining lithium mica concentrate I and tailings; the tailings are subjected to wet ball milling to obtain ore slurry II, and sequentially adding the combined depressant and the lithium mica collector to perform a one-roughing-two-scavenging-two-cleaning process, obtaining lithium mica concentrate II and lithium mica flotation tailings;

[0019] The combined depressant comprises 20-45 parts of pentasodium diethylenetriamine pentamethylene phosphonate (DTPMP), 20-45 parts of maleic acid-acrylic acid copolymer (MA / AA), and 1-20 parts of carboxymethyl cellulose (CEC).

[0020] In one preferred embodiment, the fineness of the crushed raw ore is 50%-65% of -0.074 mm.

[0021] During flotation, both the too coarse ore particles (greater than 0.1 mm) and the extremely fine ore particles (less than 0.006 mm) will cause poor flotation effect and low recovery rate.

[0022] In one preferred embodiment, the Li2O grade in the raw ore is 0.2%-0.6%.

[0023] If the raw ore grade is too low, the first-stage rough concentrate grade is often low, which brings difficulties to the second-stage flotation, and the concentrate grade is often not up to the requirements. Therefore, the flotation of the raw ore with low grade is difficult.

[0024] In one preferred embodiment, the relative content of argillaceous gangue in the raw ore is 20%-45%; the argillaceous gangue comprises one or more of calcite, kaolinite, and clay minerals.

[0025] The presence of a large amount of argillaceous gangue in the flotation ore slurry will bring a series of adverse effects to the flotation. The main effects are as follows:

[0026] ①Easy to be mixed in the foam product, the concentrate grade is reduced;

[0027] ②Easy to cover the surface of coarse particles, affecting the flotation of coarse particles;

[0028] ③Adsorb a large amount of reagents, increase the consumption of reagents;

[0029] ④Make the slurry sticky, and the aeration condition is deteriorated.

[0030] Therefore, too much argillaceous gangue leads to poor effect of most of the flotation methods disclosed in the prior art.

[0031] In one preferred embodiment, the beneficiation method has a temperature of less than 15℃.

[0032] The ionization constant K of low temperature is reduced, the concentration of anionic collector is reduced, the collecting ability is poor at low temperature, and the flotation effect is poor.

[0033] The molecular formula of diethylenetriamine pentamethylene phosphonic acid pentasodium is C9H 23 O 15 N3P5Na5, the structural formula is as follows:

[0034]

[0035] In one preferred embodiment, the structural formula of maleic acid-acrylic acid copolymer is as follows, wherein n, m = 2-10:

[0036]

[0037] In one preferred embodiment, the combined inhibitor includes 45 parts of diethylenetriamine pentamethylene phosphonic acid pentasodium, 45 parts of maleic acid-acrylic acid copolymer and 10 parts of carboxymethyl cellulose by weight.

[0038] In one preferred embodiment, the combined inhibitor includes 43 parts of diethylenetriamine pentamethylene phosphonic acid pentasodium, 43 parts of maleic acid-acrylic acid copolymer and 14 parts of carboxymethyl cellulose by weight.

[0039] In one preferred embodiment, a rough two-concentrate process flow includes:

[0040] a. Roughing I: adding 50-200g / t of combined inhibitor to the slurry, stirring for 1-2min, then adding 50-500g / t of lepidolite collector, stirring for 2-3min, scraping foam for 2-5min, to obtain rough concentrate 1, and the product in the tank is tailings for re-concentration operation;

[0041] b. Wet ball milling the rough concentrate 1 until the fineness is 70%-95% of -0.045mm;

[0042] c. twice cleaning: the ball-milled rough concentrate obtained in step b) is poured into a cleaning flotation tank, fully stirred for 0.5-1 min, and froth scraped for 2-3 min; the froth is cleaned twice, stirred for 0.5-1 min, and froth scraped for 1-2 min, to obtain a lepidolite concentrate 1, and middlings from the two cleaning operations are combined with tailings from rough selection I for re-selection.

[0043] In one preferred embodiment, the lepidolite concentrate 1 has a Li2O grade of ≥2.0%.

[0044] In one preferred embodiment, a one-rough-two-clean process includes:

[0045] d. rough selection II: the tailings and middlings obtained in the one-rough-two-clean process are combined, 1-100 g / t of a combined depressant is added, stirred for 1-2 min, 50-300 g / t of a lepidolite collector is added, stirred for 2-3 min, and froth scraped for 2-5 min, to obtain a rough concentrate 2, and the in-tank product is subjected to cleaning operation;

[0046] e. twice cleaning: 50-150 g / t of a lepidolite collector is added to the in-tank product of rough selection II, stirred for 2-3 min, and froth scraped for 1-3 min, to obtain a cleaning I product and a froth product I; the froth product I is returned to rough selection II; 30-100 g / t of a lepidolite collector is added to the cleaning I product, fully stirred for 2-3 min, and froth scraped for 1-3 min, to obtain a cleaning II product and a froth product II; the froth product II is returned to cleaning I, and the cleaning II product is tailings;

[0047] f. twice cleaning: 1-50 g / t of a combined depressant is added to the rough concentrate 2 for cleaning I operation, stirred for 1-2 min, and froth scraped for 1-3 min, to obtain a froth product III and cleaning tailings I; the froth product III is subjected to cleaning II operation, and the cleaning tailings I is returned to rough selection II operation; the froth product III is stirred and froth scraped for 1-3 min, to obtain a lepidolite concentrate 2 and cleaning tailings II, and the cleaning tailings II is returned to cleaning I operation.

[0048] In one preferred embodiment, the lepidolite concentrate 2 has a Li2O grade of ≥1.5%.

[0049] In the present application, “g / t” refers to the amount of a reagent added to lepidolite ore, for example, the amount of lepidolite collector WJ-L2 added is 400 g / t, which means that 400 g of WJ-L2 is needed to treat 1 ton of lepidolite ore.

[0050] The present application is further explained as follows:

[0051] The present application has the advantages that: ① the combined inhibitor WJ-L1 is used in combination with the lithium mica collector WJ-L2, and the recovery of lithium mica is simultaneously strengthened under low temperature and high mud content environment; ② the process flow design is "coarse grinding and coarse separation + starvation dosing - regrinding and cleaning (one rough two cleaning - two cleaning)", which can realize selective and efficient recovery of lithium mica under the condition of no desliming, can produce high-Li2O grade lithium mica concentrate 1 and secondary high-Li2O grade lithium mica concentrate 2, guarantees the production of high-Li2O grade and recovery rate of concentrate, and can solve the problems of low temperature solubility and poor dispersibility of lithium mica collector, improve the flotation recovery rate of lithium mica in winter, and realize efficient comprehensive utilization of low-grade lithium mica resources. At the same time, the stage grinding and stage flotation process can reduce the influence of high content of argillaceous gangue on lithium mica flotation, and can adapt to the fluctuation of ore properties, and guarantee the high-Li2O recovery rate. Specifically, as follows: i2 O grade lithium mica concentrate 1 and secondary high-Li2O grade lithium mica concentrate 2, guarantee the production of high-Li2O grade and recovery rate of concentrate, and can solve the problems of low temperature solubility and poor dispersibility of lithium mica collector, improve the flotation recovery rate of lithium mica in winter, and realize efficient comprehensive utilization of low-grade lithium mica resources. At the same time, the stage grinding and stage flotation process can reduce the influence of high content of argillaceous gangue on lithium mica flotation, and can adapt to the fluctuation of ore properties, and guarantee the high-Li2O recovery rate. Specifically, as follows:

[0052] (1) New process principle:

[0053] According to the characteristics of low-Li2O grade of raw ore, high-mud content of raw ore and uneven embedding of lithium mica, the present application adopts the idea of "stage grinding - stage separation".

[0054] ① Two-stage roughing: due to the interference of argillaceous gangue on lithium mica flotation, the lithium mica floating speed is slow, the roughing is set to two stages, and the Li2O recovery rate is fully guaranteed;

[0055] ② Two-stage grinding: coarse grinding and coarse separation + starvation dosing, first, coarse grinding guarantees the full floating of lithium mica and its intergrowth while avoiding argillaceous gangue as much as possible; second, insufficient amount of WJ-L2 is added in coarse separation, the strong selectivity of WJ-L2 is utilized, and the difference in floatability between lithium mica and gangue minerals is fully utilized, so that the gangue minerals can be effectively inhibited by WJ-L1; third, regrinding makes lithium mica fully dissociate, which is beneficial to the improvement of the Li2O grade of the concentrate in cleaning operation; fourth, the open circuit form is adopted, the middlings of the coarse grinding and coarse separation part are not returned, and the middlings of the cleaning are all combined into the tailings reselection roughing operation, so as to guarantee the Li2O grade of the high-lithium mica concentrate.

[0056] ③ Two concentrate products: coarse grinding and coarse separation - regrinding and cleaning produce high-Li2O grade lithium concentrate 1, and tailings reselection produces secondary high-Li2O grade lithium concentrate 2. It has strong adaptability to low-grade high-mud lithium ore, and can obtain high-Li2O grade lithium concentrate and guarantee the total concentrate Li2O recovery rate.

[0057] (2) New reagent principle:

[0058] ① Combined inhibitor WJ-L1:

[0059] DTPMP is an inhibitor for calcium-containing gangue, silicate gangue and argillaceous gangue, and has strong dispersing ability. DTPMP is adsorbed on the surface of gangue minerals by coordination of O in phosphate with Ca 2+ , Mg 2+ metal ions, preventing the adsorption of collectors and improving selectivity. MA / AA is a low molecular weight polyelectrolyte, which is copolymerized from maleic acid and acrylic acid in a certain proportion. The carboxyl groups in its molecular structure are adsorbed on the surface of gangue minerals by electrostatic force and chemical action, and the other hydroxyl groups are outward, forming a hydrophilic film. In addition, MA / AA has strong dispersing and defoaming ability of acrylic acid, which can effectively reduce the slurry viscosity of high slime system and reduce the interference of gangue on the flotation of lepidolite. MA / AA and organic phosphonate DTPMP have good compatibility and synergistic effect. Influenced by factors such as steric hindrance and electrostatic repulsion, the combined use can co-adsorb on the surface of gangue minerals, increase the adsorption area covered by the adsorption sites, and strengthen the hydrophilicity of gangue. CEC is also an effective inhibitor and slime flocculant for carbonate gangue, magnesium silicate and argillaceous gangue. The negatively charged CEC molecules are fixed on the surface of gangue minerals by hydrogen bonding, electrostatic attraction and chemical adsorption, etc., changing the surface electrical properties and making them separate from the surface of lepidolite. The other carboxyl and hydroxyl groups make the surface of gangue minerals hydrophilic by associating with water molecules. In addition, the CEC molecule has multiple active functional groups, and the molecular chain has multiple selective adsorption sites for gangue minerals, which can flocculate gangue minerals by bridging, increase the particle size and reduce the specific surface area, thereby strengthening the inhibition effect.

[0060] ②Combined collector WJ-L2:

[0061] Rice bran oil acid is an anionic surfactant, and the main components are unsaturated fatty acids (oleic acid and linoleic acid), saturated fatty acids (linolenic acid, hexadecanoic acid and octadecanoic acid), with contents of about 40%, 37%, 0.5%, 17.5% and 1.5% respectively. Compared with single oleic acid, rice bran oil acid is composed of unsaturated fatty acids and saturated fatty acids in different proportions, and has both collecting and selectivity. HOL introduces sulfate to make rice bran oil acid molecules have two active functional groups. Since both carboxyl and sulfate groups can react with the surface of minerals, the coverage area of the collector is expanded, the hydrophobicity of the mineral surface is strengthened, and the dosage of the reagent is reduced. Therefore, the collecting ability and selectivity of HOL are further enhanced; the anionic group of HSN is sulfonic acid group RO3 - , and the anionic group of HSN is sulfonic acid group RO3 - , and the anionic group of HSN is sulfonic acid group RO3 - , and the anionic group of HSN is sulfonic acid group RO3 -The co-adsorption occurs among them; the MOA is a non-ionic surfactant, by using the solubilization effect thereof, the critical micelle concentration of the complex system of the fatty acid collector and the MOA is lower, the hydrophobic part in the molecular structure of the MOA is inserted into the hydrophobic area of the fatty acid micelle to generate a mixed micelle structure with a more loose structure, the spatial steric hindrance of mutual attraction between the hydrocarbon chains of the fatty acid molecules is increased, the fatty acid molecules are prevented from forming larger clusters, the dispersibility of the fatty acid molecules under low temperature conditions is improved, and thus the low-temperature flotation performance of the collector is strengthened; the CLS is a high-molecular polymer anionic surfactant and is also a silicate and carbonate gangue mineral inhibitor, the selectivity of the collector is improved, in addition, the CLS can also disperse the slime and produce the defoaming effect, so that the flotation froth is clear and not sticky. The above-mentioned anionic and non-ionic collectors are complexed with the cationic DDA, the existence of the anionic and non-ionic collectors does not affect the adsorption of the DDA on the surface of the lepidolite, the DDA is preferentially adsorbed on the surface of the lepidolite, the negative electricity of the surface of the lepidolite is reduced, and the co-adsorption of the anionic and non-ionic collectors is facilitated. In the gangue mineral flotation system, the existence of the anionic and non-ionic collectors, the DDA preferentially reacts with the gangue minerals, and a small amount of DDA is adsorbed on the surface of the gangue minerals, and thus the efficient flotation separation of the lepidolite and the gangue minerals can be realized. In addition, the optimal pH range for the separation is expanded.

[0062] Compared with the prior art, the present application has the following beneficial effects:

[0063] (1) For the separation of low-grade high-muddy lepidolite ore, the present application designs the process flow of "coarse grinding and coarse separation + starvation dosing - regrinding and cleaning separation (one rough two cleaning two separation) - tailing reselection (one rough two cleaning two separation)", the unsaturated combined collector WJ-L2 is added in the coarse grinding and coarse separation operation, the lepidolite and its intergrowth are ensured to float up fully while the gangue is avoided to be muddy as much as possible, the lepidolite and the gangue minerals are fully dissociated through the regrinding of the concentrate, and the high-Li2O-grade concentrate product 1 is ensured to be output; the tailings are supplemented with the collector to float the lepidolite, and the sub-high-Li2O-grade concentrate product 2 is output. Through the stage grinding - stage separation, the lepidolite can be collected early, the combined inhibitor WJ-L1 and the combined collector WJ-L2 are used, the Li2O grade and the recovery rate of the concentrate are ensured, and the present application has the universality for the low-grade high-muddy lepidolite ore;

[0064] (2) In the present application, the small-molecule organic carboxylic acid MA / AA, the organic phosphonate DTPMP and the high-molecular organic inhibitor CEC can effectively inhibit the carbonate, the silicate and the muddy gangue through the synergistic effect, the selective inhibition is realized through the inhibitor effect, the surface of the gangue is stripped from the lepidolite, the surface of the gangue is strongly hydrophilic, and the gangue particles are flocculated, the lepidolite flotation environment is purified, and thus the Li2O grade in the concentrate is improved;

[0065] (3) The WJ-L2 has enhanced low-temperature solubility and dispersibility, enhanced selective collecting capacity for lepidolite, reduced viscosity of flotation froth, good flowability, less entrainment, expanded optimal separation pH range, and reduced reagent cost after the combination of anion, cation and non-ion in the present application;

[0066] (4) After the separation process and reagent system provided by the present application, for low-grade and high-mud lithium mica ore, when the Li2O grade of the raw ore is 0.2%-0.6%, the separation index of Li2O grade ≥2.0% in high-grade main concentrate 1, Li2O grade ≥1.5% in sub-high-grade concentrate 2, and total Li2O recovery rate ≥85.0% in concentrate 1 and concentrate 2 is obtained, and the economic benefit is considerable;

[0067] (5) The compounded inhibitor and collector components in the present application have the advantages of wide source, green, environmental protection, easy configuration, easy operation in industry, and practical application and promotion value. BRIEF DESCRIPTION OF DRAWINGS

[0068] Figure 1 is the process flow of Example 1, Comparative Example 1-17;

[0069] Figure 2 is the process flow of Comparative Example 18;

[0070] Figure 3 is the process flow of Comparative Example 19;

[0071] Figure 4 is the process flow of Example 2, Comparative Example 20-32;

[0072] Figure 5 is the process flow of Comparative Example 33. DETAILED DESCRIPTION

[0073] The present application will be described in detail below with reference to the accompanying drawings and in combination with examples. It should be noted that the examples in the present application and the features in the examples can be combined with each other without conflict.

[0074] A certain lithium-rubidium-tungsten-tin polymetallic ore in Jiangxi Province, the raw ore is mainly lithium-rubidium associated with tungsten-tin, the Li2O grade is low, which is 0.27%, the Rb2O, WO3 and Sn content is 0.17%, 0.041% and 0.063% respectively. Lithium-rubidium in the ore mainly exists in the form of isomorphism in iron lepidolite, tin mainly exists in the form of cassiterite, tungsten mainly exists in the form of wolframite, and lithium-tungsten-tin minerals in the ore are mainly in the form of medium-fine particle intergrowth. XRD test and mineral composition and relative content determination results show that the gangue minerals are mainly carbonates (mainly calcite), kaolinite and clay minerals, and the total relative content is more than 40%, which is easy to be pelitization in the grinding and flotation process, thereby affecting the flotation of lepidolite. Therefore, the ore belongs to low-grade high-mud lithium mica ore.

[0075] The raw ore grinding fineness is about 60% of -74 μm, and the tungsten-tin rough concentrate is selected by classification-shaking table process, the iron is removed by low intensity magnetic separation (magnetic field intensity 0.3 T), and the tailings of low intensity magnetic separation is used as the feed of lepidolite flotation (Example 1 and Comparative Examples 1-17) or high intensity magnetic separation (Comparative Example 18). ① The lepidolite concentrate 1, the lepidolite concentrate 2 and the tailings are obtained by flotation recovery of lepidolite; ② the lepidolite concentrate and the tailings are obtained by high intensity magnetic separation recovery of lepidolite. The test process is shown in detail in Figure 1 and Figure 2 This example mainly investigates the recovery of lepidolite, and the shaking table and low intensity magnetic separation are only presented in the form of common process, and are not described in detail.

[0076] The process flow of this example is shown in Figure 1 , and the specific beneficiation process and reagent system are as follows:

[0077] (1) Coarse grinding and roughing I: 50 g / t combined depressant (WJ-L1) is added to the lepidolite flotation feed, stirred for 2 min, 200 g / t lepidolite collector (WJ-L2) is added, stirred for 3 min, and scraped for 3 min to obtain rough concentrate 1, and the product in the tank is tailings for re-concentration feed;

[0078] (2) The regrinding fineness of rough concentrate 1 is 82% of -0.045 mm;

[0079] (3) Twice cleaning in coarse grinding and roughing: both the first and second cleaning are blank cleaning, the scraping time is 2 min and 1.5 min respectively, and the high Li2O grade lithium concentrate 1, middlings 1 and middlings 2 are obtained;

[0080] (4) Tailings re-concentration roughing II: the product in the tank in step (1) is combined with middlings 1 and middlings 2 in step (3), 50 g / t WJ-L1 is added, stirred for 2 min, 150 g / t WJ-L2 is added, stirred for 3 min, and aerated and scraped for 2.5 min to obtain rough concentrate 2 and scavenging feed;

[0081] (5) Tailings re-concentration scavenging I: 75 g / t WJ-L2 is added to the scavenging feed, stirred for 3 min, and scraped for 2 min, the flotation froth is scavenging concentrate 1, and the product at the tank bottom is scavenging two feed; Scavenging II: 35 g / t WJ-L2 is added to the scavenging two feed, stirred for 3 min, and scraped for 1.5 min, the flotation froth is scavenging concentrate 2, and the product in the tank is tailings;

[0082] (6) Tailings re-concentration roughing I: 25 g / t WJ-L1 is added to the rough concentrate 2, stirring for 2 min, scraping foam for 2 min, and the flotation froth is the rough concentrate II feed, and the tank tailings are the middlings 3; roughing II: blank roughing, scraping foam for 1.5 min, to obtain the secondary high Li2O grade lithium concentrate 1, and the tank bottom tailings are the middlings 4. All the middlings in the tailings re-concentration operation are returned in sequence.

[0083] The inhibitor WJ-L1 is DTPMP, MA / AA, CEC, and the mass ratio is 45 parts, 45 parts, and 10 parts; the molecular weight of MA / AA is between 450-700.

[0084] The collector WJ-L2 is HOL, HSN, DDA, MOA, and CLS, and the mass ratio is: 30 parts, 30 parts, 20 parts, 10 parts, and 10 parts;

[0085] The closed-circuit test results are shown in Table 1 as 1#.

[0086] Comparative Example 1: The process flow is the same as Example 1, except that the inhibitor is single DTPMP, and the closed-circuit test results are shown in Table 1 as 2#. The pulp pH is 7.0±0.2, and the pulp temperature is 25℃.

[0087] Roughing I: DTPMP 50 g / t; tailings re-concentration roughing II: DTPMP 50 g / t; tailings re-concentration roughing I: DTPMP 25 g / t;

[0088] Comparative Example 2: The process flow is the same as Example 1, except that the inhibitor is single MA / AA, and the closed-circuit test results are shown in Table 1 as 3#. The pulp pH is 7.0±0.2, and the pulp temperature is 25℃.

[0089] Roughing I: MA / AA 50 g / t; tailings re-concentration roughing II: MA / AA 50 g / t; tailings re-concentration roughing I: MA / AA 25 g / t;

[0090] Comparative Example 3: The process flow is the same as Example 1, except that the inhibitor is single CEC, and the closed-circuit test results are shown in Table 1 as 4#. The pulp pH is 7.0±0.2, and the pulp temperature is 25℃.

[0091] Roughing I: CEC 50 g / t; tailings re-concentration roughing II: CEC 50 g / t; tailings re-concentration roughing I: CEC 25 g / t;

[0092] Comparative Example 4: The process flow is the same as Example 1, except that the collector is single HOL, and the closed-circuit test results are shown in Table 1 as 5#. The pulp pH is 7.0±0.2, and the pulp temperature is 25℃.

[0093] Primary roughing I: HOL 200 g / t; re-concentration roughing II of tailings: HOL 150 g / t; re-concentration scavenging I of tailings: HOL 75 g / t; scavenging II: HOL 35 g / t;

[0094] Comparative Example 5: The process flow is the same as Example 1, except that the collector is single HSN, and the closed-circuit test results are shown in Table 1 as No. 6. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0095] Primary roughing I: HSN 200 g / t; re-concentration roughing II of tailings: HSN 150 g / t; re-concentration scavenging I of tailings: HSN 75 g / t; scavenging II: HSN 35 g / t;

[0096] Comparative Example 6: The process flow is the same as Example 1, except that the collector is single DDA, and the closed-circuit test results are shown in Table 1 as No. 7. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0097] Primary roughing I: DDA 200 g / t; re-concentration roughing II of tailings: DDA 150 g / t; re-concentration scavenging I of tailings: DDA 75 g / t; scavenging II: DDA 35 g / t;

[0098] Comparative Example 7: The process flow is the same as Example 1, except that the collector is single MOA, and the closed-circuit test results are shown in Table 1 as No. 8. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0099] Primary roughing I: MOA 200 g / t; re-concentration roughing II of tailings: MOA 150 g / t; re-concentration scavenging I of tailings: MOA 75 g / t; scavenging II: MOA 35 g / t;

[0100] Comparative Example 8: The process flow is the same as Example 1, except that the collector is single CLS, and the closed-circuit test results are shown in Table 1 as No. 9. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0101] Primary roughing I: CLS 200 g / t; re-concentration roughing II of tailings: CLS 150 g / t; re-concentration scavenging I of tailings: CLS 75 g / t; scavenging II: CLS 35 g / t;

[0102] Comparative Example 9: The process flow is the same as Example 1, except that the collector is a combination of HOL and DDA, and the combination ratio is the same as Example 1; the closed-circuit test results are shown in Table 1 as No. 10. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0103] Primary roughing I: HOL / DDA 200 g / t; re-concentration of tailings roughing II: HOL / DDA 150 g / t; re-concentration of tailings scavenging I: HOL / DDA 75 g / t; scavenging II: HOL / DDA 35 g / t;

[0104] Comparative Example 11: The process flow is the same as that of Example 1, except that the collector is CLS and DDA, and the combination ratio is the same as that of Example 1; the closed-circuit test results are shown in No. 12 in Table 1. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25℃.

[0105] Primary roughing I: HSN / DDA 200 g / t; re-concentration of tailings roughing II: HSN / DDA 150 g / t; re-concentration of tailings scavenging I: HSN / DDA 75 g / t; scavenging II: HSN / DDA 35 g / t;

[0106] Comparative Example 11: The process flow is the same as that of Example 1, except that the collector is CLS and DDA, and the combination ratio is the same as that of Example 1; the closed-circuit test results are shown in No. 12 in Table 1. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25℃.

[0107] Primary roughing I: CLS / DDA 200 g / t; re-concentration of tailings roughing II: CLS / DDA 150 g / t; re-concentration of tailings scavenging I: CLS / DDA 75 g / t; scavenging II: CLS / DDA 35 g / t;

[0108] Comparative Example 12: The process flow is the same as that of Example 1, except that the collector is HOL, HSN, DDA and CLS, and the combination ratio is the same as that of Example 1; the closed-circuit test results are shown in No. 13 in Table 1. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25℃.

[0109] Primary roughing I: HOL / HSN / DDA / CLS 200 g / t; re-concentration of tailings roughing II: HOL / HSN / DDA / CLS 150 g / t; re-concentration of tailings scavenging I: HOL / HSN / DDA / CLS 75 g / t; scavenging II: HOL / HSN / DDA / CLS 35 g / t;

[0110] Comparative Example 13: The process flow is the same as that of Example 1, except that the collector is HOL, HSN, DDA and CLS, and the combination ratio is the same as that of Example 1; the closed-circuit test results are shown in No. 14 in Table 1. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 15℃.

[0111] Regrinding roughing Ⅰ: HOL / HSN / DDA / CLS 200 g / t; regrinding roughing Ⅱ: HOL / HSN / DDA / CLS 150 g / t; regrinding scavenging Ⅰ: HOL / HSN / DDA / CLS 75 g / t; scavenging Ⅱ: HOL / HSN / DDA / CLS 35 g / t;

[0112] Comparative Example 14: The process flow is the same as that of Example 1, except that the collectors are HOL, HSN, DDA and CLS, and the combination ratio is the same as that of Example 1. The closed-circuit test results are shown in 15# in Table 1. The pulp pH is 7.0±0.2, and the pulp temperature is 6℃.

[0113] Regrinding roughing Ⅰ: HOL / HSN / DDA / CLS 200 g / t; regrinding roughing Ⅱ: HOL / HSN / DDA / CLS 150 g / t; regrinding scavenging Ⅰ: HOL / HSN / DDA / CLS 75 g / t; scavenging Ⅱ: HOL / HSN / DDA / CLS 35 g / t;

[0114] Comparative Example 15: The process flow is the same as that of Example 1, except that the collectors are HOL, HSN, DDA, MOA and CLS, and the combination ratio is the same as that of Example 1. The closed-circuit test results are shown in 16# in Table 1. The pulp pH is 7.0±0.2, and the pulp temperature is 6℃.

[0115] Regrinding roughing Ⅰ: HOL / HSN / DDA / MOA / CLS 200 g / t; regrinding roughing Ⅱ: HOL / HSN / DDA / MOA / CLS 150 g / t; regrinding scavenging Ⅰ: HOL / HSN / DDA / MOA / CLS 75 g / t; scavenging Ⅱ: HOL / HSN / DDA / CLS 35 g / t;

[0116] Comparative Example 16: The process flow is the same as that of Example 1, except that the collectors are sulfonated oleic acid, HSN, DDA, MOA and CLS, and the combination ratio is the same as that of Example 1. The closed-circuit test results are shown in 17# in Table 1. The pulp pH is 7.0±0.2, and the pulp temperature is 6℃.

[0117] Regrinding roughing Ⅰ: sulfonated oleic acid / HSN / DDA / MOA / CLS 200 g / t; regrinding roughing Ⅱ: sulfonated oleic acid / HSN / DDA / MOA / CLS 150 g / t; regrinding scavenging Ⅰ: sulfonated oleic acid / HSN / DDA / MOA / CLS 75 g / t; scavenging Ⅱ: HOL / HSN / DDA / CLS 35 g / t;

[0118] Comparative Example 17: The process flow is the same as that of Example 1, except that the depressant is sodium hexametaphosphate. The closed-circuit test results are shown in 18# in Table 1. The pulp pH is 7.0±0.2, and the pulp temperature is 6℃.

[0119] Coarse selection I: sodium hexametaphosphate 50 g / t; twice cleaning: blank; tailings reselection coarse selection II: sodium hexametaphosphate 50 g / t; cleaning I: sodium hexametaphosphate 25 g / t; cleaning II: blank;

[0120] Comparative example 18: Since iron-lithium mica is a weakly magnetic mineral, the weakly magnetic tailings are selected by strong magnetic separation (the strong magnetic separation test is carried out by using SLon-100 periodic impulse high gradient magnetic separator produced by Jiangxi Ganzhou Jinhuang Magnetic Separation Equipment Co., Ltd., and the strong magnetic separation process is the same as the pre-concentration of wolframite by strong magnetic separation in patent CN 104475340A), and a process flow of one coarse selection-one scavenging-one cleaning is adopted, and the middlings are sequentially returned. The process flow is as shown in Figure 2 The reagent is the same as that in example 1; the closed-circuit test results of comparative example 18 are shown in 19# in table 1.

[0121] Coarse selection: magnetic field strength is 1.8T, pulse is 6.8HZ; cleaning: magnetic field strength is 1.8T, pulse is 6.8HZ; scavenging: magnetic field strength is 1.8T, pulse is 6.8HZ.

[0122] Comparative example 19: the reagent types are the same as those in example 1, and the process flow of iron-lithium mica flotation adopts a conventional one coarse selection-two scavenging-two cleaning. The process flow is as shown in Figure 3 The closed-circuit test results of comparative example 18 are shown in 20# in table 1. The pulp pH is 7.0±0.2, and the pulp temperature is 6℃.

[0123] Coarse selection: 100g / t WJ-L1, 350g / t WJ-L2; Scavenging I: 75g / t WJ-L2; Scavenging II: 35g / t WJ-L2; Cleaning I: 25g / t; Cleaning II: blank;

[0124] Table 1: Closed-circuit test results of example 1 and comparative examples 1-19 / %

[0125]

[0126]

[0127]

[0128] Note: In table 1, the iron-lithium mica concentrate is simply referred to as concentrate, and the iron-lithium mica flotation or strong magnetic separation tailings are simply referred to as tailings.

[0129] From Table 1, ① compared with DTPMP and collector WJ-L2 (2#), MA / AA and collector WJ-L2 (3#), CEC and collector WJ-L2 (4#), WJ-L1 and collector HOL (5#), WJ-L1 and collector HSN (6#), WJ-L1 and collector DDA (7#), WJ-L1 and collector MOA (8#), WJ-L1 and collector CLS (9#), WJ-L1 and collector HOL / DDA (10#), WJ-L1 and collector HSN / DDA (11#), WJ-L1 and collector CLS / DDA (12#), WJ-L1 and collector HOL / HSN / DDA / CLS (13#), WJ-L1 and WJ-L2 combination (1#), higher Li2O grade and Li2O recovery rate can be obtained simultaneously, the Li2O grade of iron lithium mica concentrate 1+2 is 1.84%, and the total Li2O recovery rate is 88.15%; ② when WJ-L1 and HOL / HSN / DDA / CLS are used (13#-15#), the temperature is reduced from 25 DEG C to 15 DEG C and then to 6 DEG C, and the Li2O recovery rate is reduced from 82.33% to 63.57% and then to 34.58%, which shows that the low-temperature flotation effect of the collector HOL / HSN / DDA / CLS is poor; ③ when the collector WJ-L2 (16#) is used, the Li2O grade of iron lithium mica concentrate 1+2 is 1.88% and the total Li2O recovery rate is 88.01% when the pulp temperature is 6 DEG C, which shows that WJ-L2 can strengthen the recovery of iron lithium mica under low-temperature conditions; ④ when sulfonated oleic acid is used to replace sulfated rice bran oil acid in the collector WJ-L2 (17#), compared with 16#, the Li2O grade of iron lithium mica concentrate 1+2 is reduced by 0.33%, and the total Li2O recovery rate is reduced by 1.69%; when sodium hexametaphosphate is used to replace the depressant WJ-L1 (18#), compared with 16#, the Li2O grade of iron lithium mica concentrate 1+2 is reduced by 0.46%, and the total Li2O recovery rate is reduced by 1.75%, which shows that the combination of the depressant WJ-L1 and the collector WJ-L2 in the application has good collecting capacity and selectivity for lithium mica flotation, and is a high-quality flotation reagent for low-grade and high-silt lithium mica ore; ⑤ compared with 16#, when the iron lithium mica is recovered by strong magnetic separation (19#), the Li2O grade of the concentrate is reduced by 0.36%, and the Li2O recovery rate is reduced by 7.87%, which shows that for this type of ore, the silt content is high, the strong magnetic separation is seriously entrained, the silt gangue interferes with the recovery of iron lithium mica, and the recovery effect is not ideal; ⑥ compared with 16#, when WJ-L1 and WJ-L2 are combined, and the flotation process flow adopts the conventional one-roughing two-scavenging two-cleaning (20#), the Li2O grade of iron lithium mica concentrate 1+2 is reduced by 0.33%, and the total Li2O recovery rate is reduced by 8.90%, which shows that even if the new depressant WJ-L1 and the collector WJ-L2 are combined, but the flotation process flow is the conventional flow, high Li2O grade and high Li2O recovery rate iron lithium mica concentrate cannot be obtained.

[0130] Example 2

[0131] A certain alkali granite type of lepidolite mine in Yichun City, Jiangxi Province, has a low grade of Li2O in the raw ore, which is 0.35%, and Li mainly exists in the form of lepidolite. Rb, Cs, Ta and Nb in the ore all have recycling value, among which Rb and Cs are mostly selected out with lepidolite into the metallurgical process; among which Ta and Nb generally exist in the form of tantalum iron ore and niobium iron ore, which can be recycled by the combination of gravity separation and magnetic separation. The lepidolite in the raw ore is mainly embedded in the form of uneven thickness. The XRD test and the determination results of mineral composition and relative content show that the gangue minerals are mainly quartz, feldspar and the like, and also contain kaolinite, chlorite and serpentine and the like, which are easy to be argillized, and the relative content of the argillized gangue is more than 30%, which seriously interferes with the flotation of lepidolite.

[0132] The grinding fineness of the raw ore is 62% of -74 μm, iron is removed by low intensity magnetic separation (magnetic field strength is 0.3 T), the tailings of low intensity magnetic separation enter the chute operation, the chute concentrate enters the table operation, the table concentrate is a tantalum-niobium-tin concentrate, and the tailings of the chute and the table are combined as the lepidolite flotation feed (Example 2 and Comparative Examples 20-33), and the lepidolite is recovered by flotation.

[0133] The process flow of this example is shown in Figure 4 , and the specific beneficiation process and reagent system are as follows:

[0134] (1) Coarse grinding and roughing I: 100 g / t WJ-L1 is added to the lepidolite flotation feed, stirred for 2 min, 200 g / t WJ-L2 is added, stirred for 3 min, and the froth is scraped for 3.5 min to obtain coarse concentrate 1, and the product in the tank is tailings reselection feed;

[0135] (2) The regrinding fineness of coarse concentrate 1 is 87% of -0.045 mm;

[0136] (3) Two cleanings in coarse grinding and roughing: both the first and second cleanings are blank cleanings, the froth scraping time is 2 min and 2 min respectively, and high Li2O grade lithium concentrate 1, middlings 1 and middlings 2 are obtained;

[0137] (4) Tailings reselection roughing II: the product in the tank in step (1) is combined with middlings 1 and middlings 2 in step (3), 50 g / t WJ-L1 is added, stirred for 2 min, 200 g / t WJ-L2 is added, stirred for 3 min, and the froth is scraped for 3 min, to obtain coarse concentrate 2 and scavenging feed;

[0138] (5) Tailings re-election of sweep election I: to the sweep election of feed adding 100g / t WJ-L2, stirring 3min, scraping bubble 2min, the flotation froth is sweep concentrate 1, the tank bottom product is sweep election II feed; sweep election II: to the sweep election II feed adding 50g / t WJ-L2, stirring 3min, scraping bubble 1.5min, the flotation froth is sweep concentrate 2, the tank product is tailings;

[0139] (6) Tailings re-election of two times of concentration: the first and second concentration are blank concentration, the scraping bubble time is 2min, 1.5min respectively, obtaining the second high Li2O grade of lepidolite concentrate 2, middlings 3 and middlings 4; all middlings in tailings re-election operation return in order.

[0140] The inhibitor WJ-L1 is DTPMP, MA / AA, CEC, and the mass ratio is 43 parts, 43 parts, 14 parts;

[0141] The collector WJ-L2 is HOL, HSN, DDA, MOA, CLS, and the mass ratio is: 28 parts, 28 parts, 22 parts, 11 parts, 11 parts;

[0142] The closed-circuit test results are shown in Table 2 as 21#.

[0143] Comparative example 20: the process flow is the same as example 2, except that the inhibitor is single DTPMP, and the closed-circuit test results are shown in Table 1 as 22#. The pulp pH is 7.0±0.2, and the pulp temperature is 25℃.

[0144] Scavenging I: DTPMP 100g / t, tailings re-election of scavenging II: DTPMP 50g / t;

[0145] Comparative example 21: the process flow is the same as example 2, except that the inhibitor is single MA / AA, and the closed-circuit test results are shown in Table 2 as 23#. The pulp pH is 7.0±0.2, and the pulp temperature is 25℃.

[0146] Scavenging I: MA / AA 100g / t, tailings re-election of scavenging II: MA / AA 50g / t;

[0147] Comparative example 22: the process flow is the same as example 2, except that the inhibitor is single CEC, and the closed-circuit test results are shown in Table 2 as 24#. The pulp pH is 7.0±0.2, and the pulp temperature is 25℃.

[0148] Scavenging I: CEC 100g / t, tailings re-election of scavenging II: CEC 50g / t;

[0149] Comparative example 23: the process flow is the same as example 2, except that the inhibitor is single DDA, and the closed-circuit test results are shown in Table 2 as 25#. The pulp pH is 7.0±0.2, and the pulp temperature is 25℃.

[0150] Primary roughing I: DDA 200 g / t; re-concentration roughing II of tailings: DDA 200 g / t; re-concentration scavenging I of tailings: DDA 100 g / t; scavenging II: DDA 50 g / t;

[0151] Comparative Example 24: The process flow is the same as that of Example 2, except that the collector is HOL and DDA, and the combination ratio is the same as that of Example 2; the closed-circuit test results are shown as No. 26 in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0152] Primary roughing I: HOL / DDA 200 g / t; re-concentration roughing II of tailings: HOL / DDA 200 g / t; re-concentration scavenging I of tailings: HOL / DDA 100 g / t; scavenging II: HOL / DDA 50 g / t;

[0153] Comparative Example 25: The process flow is the same as that of Example 2, except that the collector is HSN and DDA, and the combination ratio is the same as that of Example 2; the closed-circuit test results are shown as No. 27 in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0154] Primary roughing I: HSN / DDA 200 g / t; re-concentration roughing II of tailings: HSN / DDA 200 g / t; re-concentration scavenging I of tailings: HSN / DDA 100 g / t; scavenging II: HSN / DDA 50 g / t;

[0155] Comparative Example 26: The process flow is the same as that of Example 2, except that the collector is CLS and DDA, and the combination ratio is the same as that of Example 2; the closed-circuit test results are shown as No. 28 in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0156] Primary roughing I: CLS / DDA 200 g / t; re-concentration roughing II of tailings: CLS / DDA 200 g / t; re-concentration scavenging I of tailings: CLS / DDA 100 g / t; scavenging II: CLS / DDA 50 g / t;

[0157] Comparative Example 27: The process flow is the same as that of Example 2, except that the collector is HOL, HSN, DDA and CLS, and the combination ratio is the same as that of Example 2; the closed-circuit test results are shown as No. 29 in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 25°C.

[0158] Primary roughing I: HOL / HSN / DDA / CLS 200 g / t; re-concentration roughing II of tailings: HOL / HSN / DDA / CLS 200 g / t; re-concentration scavenging I of tailings: HOL / HSN / DDA / CLS 100 g / t; scavenging II: HOL / HSN / DDA / CLS 50 g / t;

[0159] Comparative Example 28: The process flow is the same as that of Example 2, except that the collectors used are HOL, HSN, DDA and CLS, and the combination ratio is the same as that of Example 2. The closed-circuit test results are shown as No. 30 in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 15°C.

[0160] Coarse separation I: HOL / HSN / DDA / CLS 200 g / t; tailings re-separation coarse separation II: HOL / HSN / DDA / CLS 200 g / t; tailings re-separation scavenging I: HOL / HSN / DDA / CLS 100 g / t; scavenging II: HOL / HSN / DDA / CLS 50 g / t;

[0161] Comparative Example 29: The process flow is the same as that of Example 2, except that the collectors used are HOL, HSN, DDA and CLS, and the combination ratio is the same as that of Example 2. The closed-circuit test results are shown as No. 31 in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 6°C.

[0162] Coarse separation I: HOL / HSN / DDA / CLS 200 g / t; tailings re-separation coarse separation II: HOL / HSN / DDA / CLS 200 g / t; tailings re-separation scavenging I: HOL / HSN / DDA / CLS 100 g / t; scavenging II: HOL / HSN / DDA / CLS 50 g / t;

[0163] Comparative Example 30: The process flow is the same as that of Example 2, except that the collectors used are HOL, HSN, DDA, MOA and CLS, and the combination ratio is the same as that of Example 2. The closed-circuit test results are shown as No. 32 in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 10°C.

[0164] Coarse separation I: HOL / HSN / DDA / MOA / CLS 200 g / t; tailings re-separation coarse separation II: HOL / HSN / DDA / MOA / CLS 200 g / t; tailings re-separation scavenging I: HOL / HSN / DDA / MOA / CLS 100 g / t; scavenging II: HOL / HSN / DDA / CLS 50 g / t;

[0165] Comparative Example 31: The process flow is the same as that of Example 2, except that the collectors used are sulfonated oleic acid, HSN, DDA, MOA and CLS, and the combination ratio is the same as that of Example 2. The closed-circuit test results are shown as No. 33 in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 10°C.

[0166] Re-cleaned rough flotation I: sodium hexametaphosphate 50 g / t; Re-cleaned rough flotation II: sodium hexametaphosphate 50 g / t;

[0167] Comparative Example 32: The process flow is the same as that of Example 2, except that the depressant is sodium hexametaphosphate. The closed-circuit test results are shown as 34# in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 6°C.

[0168] Re-cleaned rough flotation I: sodium hexametaphosphate 50 g / t; Re-cleaned rough flotation II: sodium hexametaphosphate 50 g / t;

[0169] Comparative Example 33: The types of reagents are the same as those of Example 2, and the process flow of the flotation of iron-lithium mica is the conventional one-rough-two-scavenging-two-cleaning. The process flow is shown in Figure 5 The closed-circuit test results of Comparative Example 18 are shown as 35# in Table 2. The pulp pH = 7.0 ± 0.2, and the pulp temperature is 6°C.

[0170] Rough flotation: 150 g / t WJ-L1, 400 g / t WJ-L2; Scavenging I: 100 g / t WJ-L2; Scavenging II: 50 g / t WJ-L2;

[0171] Table 2: Closed-circuit test results of Example 2 and Comparative Examples 20-33

[0172]

[0173]

[0174]

[0175] Note: In Table 2, the lithium mica concentrate is simply referred to as concentrate, and the flotation tailings of iron-lithium mica are simply referred to as tailings.

[0176] From Table 2, ① compared with DTPMP and collector WJ-L2 (22#), MA / AA and collector WJ-L2 (23#), CEC and collector WJ-L2 (24#), WJ-L1 and collector DDA (25#), WJ-L1 and collector HOL / DDA (26#), WJ-L1 and collector HSN / DDA (27#), WJ-L1 and collector CLS / DDA (28#), WJ-L1 and collector HOL / HSN / DDA / CLS (29#), WJ-L1 and WJ-L2 combination (21#), higher Li2O grade and Li2O recovery rate can be obtained at the same time, the Li2O grade of iron lepidomelane concentrate 1+2 is 2.20%, and the total Li2O recovery rate is 87.94%; ② when WJ-L1 and HOL / HSN / DDA / CLS are used (29#-31#), the temperature is reduced from 25℃ to 15℃ and then to 6℃, and the Li2O recovery rate is reduced from 78.26% to 57.28% and then to 32.87%, indicating that the collector HOL / HSN / DDA / CLS has poor low-temperature resistance; ③ when the collector WJ-L2 is used (32#), the Li2O grade of iron lepidomelane concentrate 1+2 is 2.22% and the total Li2O recovery rate is 87.65% when the pulp temperature is 6℃, indicating that WJ-2 can strengthen the recovery of iron lepidomelane under low temperature conditions; ④ when sulfonated oleic acid is used instead of sulfated rice bran oil acid in the collector WJ-L2 (33#), compared with 32#, the Li2O grade of lepidomelane concentrate 1+2 is reduced by 0.44%, and the total Li2O recovery rate is reduced by 5.18%; when sodium hexametaphosphate is used instead of the depressant WJ-L1 (34#), compared with 32#, the Li2O grade of lepidomelane concentrate 1+2 is reduced by 0.56%, and the total Li2O recovery rate is reduced by 1.72%. It is indicated that the combination of the depressant WJ-L1 and the collector WJ-L2 is a high-quality flotation reagent for low-grade high-slime lepidomelane ore; ⑤ compared with 32#, when WJ-L1 and WJ-L2 are combined, the flotation process flow is one roughing-two scavenging-two cleaning (35#), the Li2O grade of lepidomelane concentrate 1+2 is reduced by 0.53%, and the total Li2O recovery rate is reduced by 8.13%, indicating that even if the new depressant WJ-L1 is combined with the collector WJ-L2, but the flotation process flow is the conventional flow, the lepidomelane concentrate with high Li2O grade and high Li2O recovery rate cannot be obtained.

[0177] Compared with Comparative Examples 1 and Comparative Examples 1-19, and Comparative Examples 2 and Comparative Examples 20-33, when the “coarse grinding-coarse separation + starvation dosing-regrinding cleaning (one roughing-two cleaning)-tailings reselection (one roughing-two scavenging-two cleaning)” process flow and the reagent system of WJ-L1 and WJ-L2 are used at the same time, the low-grade high-slime lepidomelane ore has the best separation effect, and the low-temperature resistance is the best, the foam is clear and refreshing, the gangue is less entrained, and the like.

[0178] The above embodiments should be understood as being used only for more clearly illustrating the present application, and should not be used for limiting the scope of the present application, and after reading the present application, various equivalent modifications of the present embodiments made by those skilled in the art all fall within the scope defined by the claims of the present application.

Claims

1. A mineral processing method, characterized in that, Includes the following steps: 1) Grinding: Take an appropriate amount of crushed raw ore and perform wet ball milling to obtain slurry I; 2) Flotation: Combined inhibitors and lepidolite collectors are added to pulp I in sequence, and a roughing and cleaning process is carried out to obtain lepidolite concentrate 1 and tailings; the tailings are then wet-milled to obtain pulp II, and combined inhibitors and lepidolite collectors are added in sequence to carry out a roughing, scavenging and cleaning process to obtain lepidolite concentrate II and lepidolite flotation tailings. The combined inhibitor, by weight, comprises 20-45 parts of diethylenetriamine pentamethylphosphonate pentasodium (DTPMP), 20-45 parts of maleic acid-acrylic acid copolymer (MA / AA), and 1-20 parts of carboxyethyl cellulose (CEC). The lepidolite collector, by weight, comprises 10-40 parts of sulfated rice bran oleic acid, 10-40 parts of sodium diisooctyl succinate sulfonate, 10-30 parts of dodecylamine, 10-20 parts of isomeric decaol polyoxyethylene ether, and 10-30 parts of calcium lignosulfonate.

2. The mineral processing method according to claim 1, characterized in that, The sulfated rice bran oleic acid is obtained by sulfated rice bran oleic acid, and the rice bran oleic acid includes 35-45 parts of oleic acid, 35-40 parts of linoleic acid, 0.1-1.0 parts of linolenic acid, 15-20 parts of hexadecanoic acid and 1-2 parts of octadecanoic acid.

3. The mineral processing method according to claim 1, characterized in that, The lepidolite collector comprises 30 parts of sulfated rice bran oleic acid, 30 parts of sodium diisooctyl succinate sulfonate, 20 parts of dodecylamine, 10 parts of isomeric decayl alcohol polyoxyethylene ether, and 10 parts of calcium lignosulfonate.

4. The mineral processing method according to claim 1, characterized in that, The raw ore has a Li2O grade of 0.2%-0.6% and a relative content of argillaceous gangue of 20%-45%. The argillaceous gangue includes one or more of calcite, kaolinite, and clay minerals. The beneficiation temperature is below 15℃.

5. The mineral processing method according to claim 1, characterized in that, The structural formula of the maleic acid-acrylic acid copolymer is as follows: ； Where n, m = 2 - 10.

6. The mineral processing method according to claim 1, characterized in that, The roughing and finishing process includes: a. Roughing I: Add 50-200 g / t of combined inhibitor to slurry I, stir for 1-2 min, then add 50-500 g / t of lepidolite collector, stir for 2-3 min, skim the foam for 2-5 min to obtain rough concentrate 1. The product in the tank is tailings for further processing. b. Wet ball mill the crude concentrate 1 until the fineness is -0.045 mm, accounting for 70%-95%; c. Two-stage refining: Pour the ball-milled rough concentrate obtained in step b) into the refining flotation cell, stir thoroughly for 0.5-1 min, and skim off the bubbles for 2-3 min; perform a second refining on the foam, stir for 0.5-1 min, and skim off the bubbles for 1-2 min to obtain lepidolite concentrate 1. The middlings from the two refining processes are incorporated into the tailings of roughing I for further refining.

7. The mineral processing method according to claim 6, characterized in that, The Li2O grade in lepidolite concentrate 1 is ≥2.0%.

8. The mineral processing method according to claim 1, characterized in that, The process flow of roughing, sweeping, and finishing includes: d. Roughing II: Combine the tailings and middlings obtained from the first roughing and second cleaning process, add 1-100 g / t of combined inhibitor, stir for 1-2 min, then add 50-300 g / t of lepidolite collector, stir for 2-3 min, and skim the bubbles for 2-5 min to obtain rough concentrate 2. The product in the tank is then subjected to scavenging operation. e. Two scavenging processes: Add 50-150 g / t lepidolite collector to the product in the roughing stage II tank, stir for 2-3 min, skim off the foam for 1-3 min, and perform scavenging I to obtain scavenging I product and foam product I; foam product I is returned to roughing stage II; add 30-100 g / t lepidolite collector to the product in scavenging I, stir thoroughly for 2-3 min, skim off the foam for 1-3 min, and perform scavenging II to obtain scavenging II product and foam product II; foam product II is returned to scavenging I, and the product in scavenging II is tailings; f. Two-stage refining: Add 1-50 g / t of combined inhibitor to rough concentrate 2 for refining operation I, stir for 1-2 min, and skim off the foam for 1-3 min to obtain foam product III and refined tailings I; foam product III enters refining operation II, and refined tailings I is returned to roughing operation II; after stirring foam product III, skim off the foam for 1-3 min to obtain lepidolite concentrate 2 and refined tailings II, and refined tailings II is returned to refining operation I.

9. The mineral processing method according to claim 8, characterized in that, The Li2O grade in lepidolite concentrate 2 is ≥1.5%.

Images