A collector for fluorite and lepidolite in tailings and a preparation method and use thereof

Abstract

The present application relates to a kind of tailings fluorite and lithium mica collector and its preparation method and purposes, the collector is made of sulfonated oleic acid, fatty amine, diesel and sodium dodecyl sulfate.The purposes include using the collector from tailings fluorite and lithium mica is recovered using flotation process;Specifically include the following processes:(1) to tailings slurry is added to the collector and is coarsely selected, and fluorite and lithium mica rough concentrate and tailings are obtained;(2) to the fluorite and lithium mica concentrate is added to inhibitor and is finely selected, and fluorite and lithium mica concentrate are obtained;The inhibitor is tannin, citric acid and lignin xanthate.By improving flotation reagent and process, overcome the fluorite and lithium mica respectively in prior art flotation recovery process long, reagent variety, recovery rate low and other difficult problems, realize the efficient recovery of fluorite and lithium mica resources in tailings, improve the resource utilization of fluorite and lithium mica.

Description

Technical Field

[0001] The present invention relates to the field of mineral processing, in particular to a collector for fluorite and lepidolite in tailings, a preparation method and application thereof, and in particular to a collector for flotation of fluorite and lepidolite from tailings, a preparation method and application thereof. Background Art

[0002] Fluorspar, also known as fluorspar, fluorspar powder, or fluorite powder, is an isometric mineral primarily composed of calcium fluoride (CaF2) and is a primary fluorine raw material. As demand for fluorine increases, high-grade single-type fluorspar ore resources are becoming increasingly depleted. Therefore, maximizing the utilization of associated (or para-)existing fluorspar, particularly in polymetallic tailings, has become a pressing challenge for the development of the fluorine industry. Flotation is the primary fluorspar beneficiation method.

[0003] Lithium is the lightest metallic element and is widely used in new energy, ceramics, aerospace, medicine, national defense, and other fields. Therefore, improving the utilization rate of lepidolite resources is of great significance to promoting the high-quality development of the lithium industry.

[0004] There are many existing methods for recovering fluorite by flotation. For example, CN104399592A discloses a fluorite flotation process, which includes the following steps: using low-grade fluorite ore as raw material, linoleic acid, peanut oil, and sodium dodecylsulfonate as collectors, adding sulfuric acid, water glass, hydrofluoric acid, and the collector in sequence during the selection process, and flotating three times to obtain flotated fluorite. CN107790290A discloses a beneficiation method for recovering fluorite from scheelite crude concentrate, which includes the following steps: pre-selecting the scheelite crude concentrate with inhibitor water glass, adding collector NAK for rough selection, and adding inhibitor acidified water glass for ten selections. CN103316773A discloses a fluorite flotation method, which includes one rough selection, one scavenging selection, nine selections, and the sequential return of the middlings; saponified oleic acid is used as the collector during the flotation process; and salted water glass (15 parts of water glass, 10 parts of sodium hexametaphosphate, 2 parts of tannin extract, and 245 parts of water) is used as the inhibitor. CN105289848A discloses a fluorite flotation method, which uses fluorite ore as raw material, modified oleic acid ionic liquid as collector, water glass as inhibitor, sodium carbonate as pH regulator, and adopts XFD series flotation machine with a volume of 1.5L for roughing.

[0005] Flotation is the primary method for beneficiating lepidolite. For example, CN111151381A discloses a cationic temperature-sensitive collector for the flotation of ore with a Li₂O content of 1.2-1.8% and lacking the characteristic characteristics of lepidolite, primarily derived from cave-mined lepidolite ores. This cationic temperature-sensitive collector is prepared by copolymerizing two monomers, N-isopropylacrylamide (NIPAM) and N-[3-dimethylaminopropyl]methacrylamide (DMAPMA), via free radical polymerization, with a molar ratio of 1:5-8:1. This cationic temperature-sensitive collector demonstrates excellent flotation performance for ore with a Li₂O content of 1.2-1.8% and lacking the characteristic characteristics of lepidolite, primarily derived from cave-mined lepidolite ores.

[0006] At present, fluorite and lepidolite are usually recovered separately in industry. The method of flotation fluorite to suppress mica is long, with many reagents and low recovery rate. In order to improve the grade of fluorite and lepidolite concentrate, inhibitors such as water glass and acidified water glass are usually added, which results in disadvantages such as difficulty in settling tailings and acid corrosion. Wu Xiqing et al. (Wu Xiqing, Hu Cong, Li Guoping, et al. Study on flotation separation of fluorite and phlogopite [J]. Non-metallic Minerals, 2012, 35(3):5.) studied the flotation separation of fluorite and phlogopite. The actual ore containing 22.27% fluorite and 75% phlogopite was subjected to a reagent system of 10.00 kg sodium carbonate, 20 kg sodium sulfide, and 0.13 kg sodium oleate. After a first-stage roughing, a fluorite lepidolite rough concentrate containing 55.40% CaF2 was obtained with a recovery rate of 88.01%. Zhou Xiaotong et al. (Zhou Xiaotong, Deng Lihong. Research on flotation separation of fluorite, calcite and mica [J]. Materials Research and Application, 2006, 16 (004): 8-11.) In view of the fact that fluorite in a mine in southern Hunan is closely interbedded with carbonaceous calcite and scaly sericite, and there are fine-grained calcite inclusions in the fluorite, it is very difficult to improve the grade of fluorite lepidolite concentrate. After experimental research, oleic acid T was selected as the collector and the combination reagent NC+TT, the combination reagent NA+TH and the TD reagent were selected as the adjusting agents. When the flotation fluorite feed grade was 43.95%, containing 14.03% CaCO3 and 13.51% SiO2, after one roughing and nine finishing, the fluorite lepidolite concentrate with a grade of 97.50% (containing 0.93% CaCO3 and 0.89% SiO2) and a recovery rate of 80.97% was obtained.

[0007] Therefore, it is of great significance to develop environmentally friendly and efficient collectors for fluorite and lepidolite, improve the resource utilization rate of fluorite and lepidolite, and avoid the use of inhibitors such as water glass and acidified water glass. Summary of the Invention

[0008] In view of the problems existing in the prior art, the object of the present invention is to provide a collector for fluorite and lepidolite in tailings, a preparation method and use thereof. By improving the flotation reagent and process, the present invention overcomes the defects of the prior art such as long flotation recovery process of fluorite and lepidolite, multiple reagent types and low recovery rate. At the same time, the drawbacks of using water glass and acidified water glass, such as difficulty in settling tailings and acid corrosion, are overcome. The present invention achieves efficient recovery of fluorite and lepidolite resources in tailings and improves the resource utilization rate of fluorite and lepidolite.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a collector for fluorite and lepidolite in tailings, wherein the collector is composed of sulfonated oleic acid, fatty amine, diesel and sodium lauryl sulfate.

[0011] The invention improves the formula of the collector and obtains the collector by utilizing a combination of sulfonated oleic acid, fatty amine, diesel and sodium dodecyl sulfate to achieve the synchronous collection of fluorite and lepidolite. The invention utilizes the synergistic effect of anion and cation coordination among the sulfonated oleic acid, fatty amine and sodium dodecyl sulfate and surfactant emulsification to achieve efficient collection of lepidolite and fluorite in the ore pulp. Simultaneously, diesel and sodium dodecyl sulfate are used to adjust foam to form a secondary enrichment effect, thereby improving the grade of the coarse concentrate. The synergistic effect among the reagents is used to achieve the recovery of fluorite and lepidolite resources from the tailings. The present invention also improves the selection agent, and utilizes a combination of tannic acid, citric acid and lignin xanthate to obtain a gangue inhibitor, wherein appropriate amounts of tannic acid and citric acid have a significant inhibitory effect on carbonate gangue, and the synergistic effect between tannic acid and lignin xanthate has a good inhibitory effect on silicate gangue. During the selection process, the inhibitory effect on gangue minerals is simultaneously enhanced, thereby improving the separation effect of fluorite and lepidolite from carbonate and silicate gangue minerals, and can obtain fluorite and lepidolite concentrates with high grade and recovery rate.

[0012] The tailings targeted in the present invention may be copper-tungsten polymetallic ore flotation tailings, the main gangue minerals of which are chalcite and feldspar, with small amounts of fluorite, lepidolite, muscovite, chlorite, kaolinite, calcite, and trace amounts of apatite, rutile, and pyroxene. Small amounts of xanthate, chelating collector, and 2# oil foaming agent may remain in the tailings.

[0013] As a preferred technical solution of the present invention, the mass ratio of sulfonated oleic acid, fatty amine, diesel and sodium lauryl sulfate in the collector is (4-6):(2-3):1:1, for example, it can be 4:2:1:1, 5:2:1:1, 6:2:1:1, 4:3:1:1, 5:3:1:1 or 6:3:1:1, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0014] As a preferred technical solution of the present invention, the fatty amine includes one or a combination of at least two of laurylamine, octadecylamine or coconut amine.

[0015] In a second aspect, the present invention provides a method for preparing the collector as described in the first aspect, the preparation method comprising mixing sulfonated oleic acid, fatty amine, diesel and sodium lauryl sulfate according to a formula.

[0016] In a third aspect, the present invention provides a use of the collector according to the first aspect, wherein the use comprises using the collector to recover fluorite and lepidolite from tailings using a flotation process;

[0017] The specific process includes the following:

[0018] (1) adding the collector to the tailings slurry for rough separation to obtain fluorite and lepidolite coarse concentrate and tailings;

[0019] (2) adding an inhibitor to the fluorite and lepidolite concentrate for beneficiation to obtain the fluorite and lepidolite concentrate;

[0020] The inhibitors are tannic acid, citric acid and lignin xanthate.

[0021] As a preferred technical solution of the present invention, the pH value of the tailings slurry in step (1) is 10.5-12, for example, it can be 10.5, 11, 11.5 or 12, etc., but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0022] In the present invention, the limitation on the pH value of the tailings slurry may be the original pH value of the tailings slurry, or the pH value after the pH value of the tailings slurry is adjusted.

[0023] Preferably, in the tailings slurry of step (1), the particles of -0.074 mm account for 50-90% of the mass of the total solid particles, for example, it can be 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88% or 90%, etc., but are not limited to the listed values, and other values ​​not listed within this range are equally applicable.

[0024] As a preferred technical solution of the present invention, the addition amount of the collector in the rough selection in step (1) is 200-800g / t, for example, it can be 200g / t, 250g / t, 300g / t, 350g / t, 400g / t, 450g / t, 500g / t, 550g / t, 600g / t, 650g / t, 700g / t, 750g / t or 800g / t, etc., but is not limited to the listed values, and other values ​​not listed within this range are equally applicable.

[0025] Preferably, the roughing in step (1) is performed at least once;

[0026] According to the present invention, the amount of collector added in the roughing process is the total amount of the reagent added. For example, if two roughing processes are performed, the total amount of collector added in the two roughing processes is 200-800 g / t.

[0027] Preferably, the tailings obtained in step (1) are subjected to at least one scavenging process;

[0028] Preferably, 50-100 g / t of collector is added during the sweeping, for example, 50 g / t, 60 g / t, 70 g / t, 80 g / t, 90 g / t or 100 g / t, etc., but not limited to the listed values, and other values ​​not listed within the range are also applicable.

[0029] In the present invention, the amount of collector added during the above-mentioned scavenging process is the total amount of the reagent added. For example, if two scavenging processes are performed, the total amount of collector added during the two scavenging processes is 50-100 g / t.

[0030] As a preferred technical solution of the present invention, the mass ratio of tannic acid, citric acid and lignin xanthate in the inhibitor in step (2) is (9-12):(1-3):1, for example, it can be 9:1:1, 10:1:1, 11:1:1, 12:1:1, 9:2:1, 10:2:1, 11:2:1, 12:2:1, 9:3:1, 10:3:1, 11:3:1 or 12:3:1, but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0031] Preferably, the amount of inhibitor added in the concentration in step (2) is 180-650 g / t, for example, it can be 180 g / t, 200 g / t, 250 g / t, 300 g / t, 350 g / t, 400 g / t, 450 g / t, 500 g / t, 550 g / t, 600 g / t or 650 g / t, but is not limited to the listed values. Other values ​​not listed within this range are also applicable.

[0032] As a preferred technical solution of the present invention, the selection in step (2) is performed at least 7 times, for example, 7 times, 8 times or 9 times, etc., but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0033] In the present invention, the amount of gangue inhibitor added during the above-mentioned beneficiation process is the total amount of the reagent added. For example, if seven beneficiations are performed, the total amount of gangue inhibitor added during the seven beneficiations is 180-650 g / t.

[0034] Preferably, when the selection in step (2) is performed for the first time, the amount of the inhibitor added is 100-200 g / t, for example, 100 g / t, 110 g / t, 120 g / t, 130 g / t, 140 g / t, 150 g / t, 160 g / t, 170 g / t, 180 g / t, 190 g / t or 200 g / t, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0035] Preferably, when the selection in step (2) is performed for the second time, the amount of the inhibitor added is 70-150 g / t, for example, 70 g / t, 80 g / t, 90 g / t, 100 g / t, 110 g / t, 120 g / t, 130 g / t, 140 g / t or 150 g / t, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0036] Preferably, when the refinement in step (2) is performed for the third time, the amount of the inhibitor added is 50-100 g / t, for example, 50 g / t, 60 g / t, 70 g / t, 80 g / t, 90 g / t or 100 g / t, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0037] Preferably, when the selection in step (2) is performed for the fourth time, the amount of the inhibitor added is 30-70 g / t, for example, 30 g / t, 35 g / t, 40 g / t, 45 g / t, 50 g / t, 55 g / t, 60 g / t, 65 g / t or 70 g / t, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0038] Preferably, when the cleaning in step (2) is performed for the fifth time, the added amount of the inhibitor is 20-50 g / t, for example, it can be 20 g / t, 22 g / t, 24 g / t, 26 g / t, 28 g / t, 30 g / t, 32 g / t, 34 g / t, 36 g / t, 38 g / t, 40 g / t, 42 g / t, 44 g / t, 46 g / t, 48 g / t or 50 g / t, but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0039] Preferably, when the cleaning in step (2) is performed for the sixth time, the amount of the inhibitor added is 10-30 g / t, for example, 10 g / t, 12 g / t, 14 g / t, 16 g / t, 18 g / t, 20 g / t, 22 g / t, 24 g / t, 26 g / t, 28 g / t or 30 g / t, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0040] Preferably, when the selection in step (2) is performed for the seventh time, the amount of the inhibitor added is 5-15 g / t, for example, 5 g / t, 6 g / t, 7 g / t, 8 g / t, 9 g / t, 10 g / t, 11 g / t, 12 g / t, 13 g / t, 14 g / t or 15 g / t, etc., but is not limited to the listed values, and other values ​​not listed within this range are also applicable.

[0041] In the present invention, the amount of gangue inhibitor added in the first seven rounds of selection is given above. Due to space limitations and for the sake of simplicity, the present invention does not specifically limit the amount of gangue inhibitor added when the selection exceeds seven times, and the specific amount should be selected according to actual conditions.

[0042] Preferably, the middlings obtained from the concentration in step (2) are sequentially returned to the previous operation.

[0043] As a preferred technical solution of the present invention, the use includes the following process:

[0044] (1) adding the collector to the tailings slurry for rough separation to obtain fluorite and lepidolite coarse concentrate and tailings;

[0045] (2) adding an inhibitor to the fluorite and lepidolite concentrate for beneficiation to obtain the fluorite and lepidolite concentrate;

[0046] The pH value of the tailings slurry in step (1) is 10.5-12; the particles of -0.074 mm in the tailings slurry account for 50-90% of the total solid particle mass; the amount of collector added in the roughing is 200-800 g / t; the roughing is performed at least once; the obtained tailings are scavenged at least once, and 50-100 g / t of collector is added in the scavenging;

[0047] The inhibitors in the step (2) are tannic acid, citric acid and lignin xanthate, the mass ratio of the tannic acid, citric acid and lignin xanthate is (9-12):(1-3):1, the adding amount of the inhibitors in the concentration is 180-650g / t; the concentration is carried out at least 7 times, the adding amount of the inhibitors is 100-200g / t when the concentration is carried out for the first time, the adding amount of the inhibitors is 70-150g / t when the concentration is carried out for the second time, the adding amount of the inhibitors is 50-100g / t when the concentration is carried out for the third time, the adding amount of the inhibitors is 30-70g / t when the concentration is carried out for the fourth time, the adding amount of the inhibitors is 20-50g / t when the concentration is carried out for the fifth time, the adding amount of the inhibitors is 10-30g / t when the concentration is carried out for the sixth time, the adding amount of the inhibitors is 5-15g / t when the concentration is carried out for the seventh time, and the middle ore obtained by the concentration is sequentially returned to the previous operation.

[0048] In the present application, the adding amount of the reagent g / t refers to adding a certain amount of reagent based on the mass t of the solid in the tailings for flotation.

[0049] Compared with the prior art, the present application has the following beneficial effects:

[0050] (1) The present application improves the formula of the roughing reagent, uses the combination of sulfonated oleic acid, fatty amine, diesel oil and sodium dodecyl sulfate to obtain a collector, and realizes the simultaneous recovery of fluorite and lepidolite resources from tailings through the synergistic effect of the reagents.

[0051] (2) The present application adds a combination of tannic acid, citric acid and lignin xanthate inhibitors in the fluorite concentration process, uses the synergistic effect of the reagents to improve the separation effect of fluorite and lepidolite from carbonate and silicate gangue minerals, and can obtain fluorite and lepidolite concentrates with high grade and high recovery rate, the calcium fluoride content in the obtained concentrate product is ≥95.03%, the lithium oxide content is ≥1.09%, and the recovery rates are ≥75.60% and ≥46.89%, respectively.

[0052] (3) The present application overcomes the defects of long process, multiple reagents and low recovery rate in the prior art of fluorite and lepidolite flotation recovery, and overcomes the disadvantages of difficult tailings settlement caused by the use of water glass and acidified water glass, acid corrosion, etc., realizes the efficient recovery of fluorite and lepidolite resources in tailings, and improves the resource utilization rate of fluorite and lepidolite. BRIEF DESCRIPTION OF DRAWINGS

[0053] Figure 1 is the flotation process flow chart of the embodiment 1 of the present application.

[0054] The present invention is further described in detail below. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims. DETAILED DESCRIPTION

[0055] To better illustrate the present invention and facilitate understanding of the technical solutions of the present invention, typical but non-limiting embodiments of the present invention are as follows:

[0056] Example 1

[0057] This embodiment specifically provides a solution for flotation of fluorite and lepidolite from tailings, using the composite collector of the present invention for flotation, as follows:

[0058] A tailings contains CaF2 8.34%, Li2O 0.11%, SiO2 49.76%. The flotation process adopts a one-roughing, one-sweeping, seven-fines process, in which the middlings from the first cleaning and scavenging are returned to the roughing, and the middlings from the second, third, fourth, fifth, sixth, and seventh cleaning are returned to the previous cleaning in sequence. Figure 1 shown.

[0059] Flotation is carried out in the following steps:

[0060] (1) adding 500 g / t of sodium hydroxide to the tailings to adjust the slurry to a pH value of 11, then adding 500 g / t of a collector, and obtaining a foam product fluorite lepidolite coarse concentrate and tailings after a rough selection, wherein the sulfonated oleic acid, dodecylamine, diesel and sodium lauryl sulfate are configured in a mass ratio of 4:2:1:1 and mixed before use;

[0061] (2) The tailings obtained after the roughing in step (1) are subjected to a scavenging process, wherein the amount of collector added during the scavenging process is 60 g / t, and the middlings obtained after the scavenging are sequentially returned to the previous operation for roughing;

[0062] (3) adding a gangue inhibitor to the fluorite lepidolite coarse concentrate obtained in step (1), wherein the gangue inhibitor is tannic acid, citric acid and lignin sodium xanthate configured in a mass ratio of 10:2:1 and mixed for use, and performing 7 selections, wherein 150 g / t of gangue inhibitor is added to the first selection, 100 g / t of gangue inhibitor is added to the second selection, 80 g / t of gangue inhibitor is added to the third selection, 60 g / t of gangue inhibitor is added to the fourth selection, 40 g / t of gangue inhibitor is added to the fifth selection, 25 g / t of gangue inhibitor is added to the sixth selection, and 15 g / t of gangue inhibitor is added to the seventh selection, and a fluorite-lepidolite concentrate product is obtained after the selection is completed.

[0063] After detection, the finally obtained closed-circuit test index is: the fluorite-lithium mica concentrate contains CaF2 95.32%, Li2O 1.09%, and the recovery rates of CaF2 and Li2O are 77.75% and 66.54% respectively.

[0064] Example 2

[0065] The embodiment specifically provides a scheme for floating fluorite and lithium mica in tailings, and the scheme adopts the compound collector in the application for floating, and the specific process is as follows:

[0066] The tailings contain CaF2 2.77%, Li2O 0.08%, and SiO2 47.78%, and the flotation process adopts a roughing-one-scavenging-eight-cleaning process, wherein the middlings of the first cleaning and scavenging are returned to roughing, and the middlings obtained in the second, third, fourth, fifth, sixth, seventh and eighth cleanings are returned to the previous cleaning in turn.

[0067] The flotation is specifically performed according to the following steps:

[0068] (1) 1000g / t of sodium hydroxide is added to the tailings to adjust the pH value to 12, and then 400g / t of the collector is added, and after once roughing, the frothy product fluorite-lithium mica rough concentrate and tailings are obtained, wherein the sulfonated oleic acid, octadecylamine, diesel oil and sodium dodecyl sulfate are mixed according to a mass ratio of 5:2:1:1;

[0069] (2) The tailings obtained after the roughing of step (1) are subjected to once scavenging, and the addition amount of the collector in the scavenging process is 80g / t, and the middlings obtained after the scavenging are sequentially returned to the previous operation for roughing;

[0070] (3) The fluorite-lithium mica rough concentrate obtained in step (1) is added with a gangue depressant, the gangue depressant is tannin acid, citric acid and potassium lignosulfonate mixed according to a mass ratio of 10:1:1, and eight cleanings are performed, wherein 160g / t of the gangue depressant is added in the first cleaning, 130g / t of the gangue depressant is added in the second cleaning, 90g / t of the gangue depressant is added in the third cleaning, 70g / t of the gangue depressant is added in the fourth cleaning, 50g / t of the gangue depressant is added in the fifth cleaning, 30g / t of the gangue depressant is added in the sixth cleaning, 10g / t of the gangue depressant is added in the seventh cleaning, and 8g / t of the gangue depressant is added in the eighth cleaning, and the fluorite-lithium mica concentrate product is obtained after the cleanings.

[0071] After detection, the finally obtained closed-circuit test index is: the fluorite-lithium mica concentrate contains CaF2 95.03%, Li2O 1.57%, and the recovery rates of CaF2 and Li2O are 75.60% and 46.89% respectively.

[0072] Example 3

[0073] The embodiment specifically provides a scheme for floating fluorite and lepidolite in tailings, and the scheme adopts the compound collector in the embodiment to perform flotation, and the specific process is as follows.

[0074] The tailings contain 3.08% of CaF2, 0.09% of Li2O and 48.27% of SiO2, and the flotation process adopts a one-roughing-one-scavenging-eight-cleaning process, wherein the middlings of the first cleaning and scavenging are returned to roughing, and the middlings obtained by the second, third, fourth, fifth, sixth, seventh and eighth cleanings are returned to the previous cleaning in turn.

[0075] The flotation is specifically performed according to the following steps.

[0076] (1) 400 g / t of sodium hydroxide is added to the tailings to adjust the pH value to 10.5, and then 450 g / t of the collector is added, and after one roughing, the frothy product fluorite lepidolite rough concentrate and tailings are obtained, wherein the sulfonated oleic acid, coconut amine, diesel oil and sodium dodecyl sulfate are mixed according to a mass ratio of 5:3:1:1.

[0077] (2) The tailings obtained after the roughing of step (1) are subjected to one scavenging, and the addition amount of the collector in the scavenging process is 70 g / t, and the middlings obtained after the scavenging are sequentially returned to the previous operation for roughing;

[0078] (3) The fluorite lepidolite rough concentrate obtained in step (1) is added with a gangue depressant, the gangue depressant is tannin acid, citric acid and potassium lignosulfonate mixed according to a mass ratio of 10:2:1, and eight cleanings are performed, wherein 180 g / t of the gangue depressant is added in the first cleaning, 140 g / t of the gangue depressant is added in the second cleaning, 90 g / t of the gangue depressant is added in the third cleaning, 70 g / t of the gangue depressant is added in the fourth cleaning, 40 g / t of the gangue depressant is added in the fifth cleaning, 30 g / t of the gangue depressant is added in the sixth cleaning, 15 g / t of the gangue depressant is added in the seventh cleaning, and 7 g / t of the gangue depressant is added in the eighth cleaning, and the fluorite lepidolite concentrate product is obtained after the cleanings.

[0079] After detection, the closed-circuit test index of the finally obtained fluorite lepidolite concentrate is as follows: CaF2 95.11%, Li2O 1.65%, and the recovery rates of CaF2 and Li2O are 77.21% and 48.46% respectively.

[0080] Example 4

[0081] The difference from the embodiment 1 is that the sulfonated oleic acid in the collector is replaced by an equal amount of oleic acid.

[0082] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains CaF2 93.52% and Li2O 1.02%, and the CaF2 and Li2O recovery rates are 74.02% and 62.54% respectively.

[0083] Example 5

[0084] The only difference from Example 1 is that the dodecylamine in the collector is replaced by an equal amount of etheramine.

[0085] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 94.52% CaF2 and 0.92% Li2O, and the recovery rates of CaF2 and Li2O are 74.80% and 57.02% respectively.

[0086] Example 6

[0087] The only difference from Example 1 is that the diesel in the collector is replaced with an equal amount of kerosene.

[0088] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 94.06% CaF2 and 0.94% Li2O, and the recovery rates of CaF2 and Li2O are 73.68% and 57.15% respectively.

[0089] Example 7

[0090] The only difference from Example 1 is that the sodium lauryl sulfate in the collector is replaced by an equal amount of sodium lauryl sulfonate.

[0091] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains CaF2 94.42% and Li2O 1.02%, and the CaF2 and Li2O recovery rates are 74.78% and 62.63% respectively.

[0092] Example 8

[0093] The only difference from Example 1 is that the sodium dodecyl sulfate in the collector is replaced by an equal amount of sodium dodecylbenzenesulfonate.

[0094] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains CaF2 94.37% and Li2O 1.01%, and the CaF2 and Li2O recovery rates are 74.69% and 62.40% respectively.

[0095] Example 9

[0096] The only difference from Example 1 is that the sodium lauryl sulfate in the collector is replaced by an equal amount of dodecyltrimethylammonium bromide.

[0097] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 94.57% CaF2 and 1.03% Li2O, and the recovery rates of CaF2 and Li2O are 72.52% and 62.09% respectively.

[0098] Example 10

[0099] The only difference from Example 1 is that the collector does not contain diesel, ensuring that the added amount remains unchanged.

[0100] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 92.17% CaF2 and 0.97% Li2O, and the recovery rates of CaF2 and Li2O are 77.19% and 62.93% respectively.

[0101] Example 11

[0102] The only difference from Example 1 is that the collector does not contain sodium lauryl sulfate, ensuring that the added amount remains unchanged.

[0103] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 94.17% CaF2 and 0.99% Li2O, and the recovery rates of CaF2 and Li2O are 73.59% and 60.47% respectively.

[0104] Example 12

[0105] The only difference from Example 1 is that the gangue inhibitor selected is acidified water glass, which is a combination of sulfuric acid and water glass in a mass ratio of 1:2. Others are the same as Example 1.

[0106] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 94.67% CaF2 and 0.94% Li2O, and the recovery rates of CaF2 and Li2O are 72.54% and 57.25% respectively.

[0107] Example 13

[0108] The only difference from Example 1 is that the citric acid in the inhibitor is replaced by an equal amount of sodium nitrohumate.

[0109] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 94.14% CaF2 and 0.98% Li2O, and the recovery rates of CaF2 and Li2O are 72.43% and 57.76% respectively.

[0110] Example 14

[0111] The only difference from Example 1 is that the lignin xanthate in the inhibitor is replaced by an equal amount of tartaric acid.

[0112] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 93.34% CaF2 and 0.95% Li2O, and the recovery rates of CaF2 and Li2O are 72.59% and 58.42% respectively.

[0113] Example 15

[0114] The only difference from Example 1 is that the lignin xanthate in the inhibitor is replaced by an equal amount of water glass (module of 2).

[0115] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains CaF2 88.31% and Li2O 0.85%, and the CaF2 and Li2O recovery rates are 77.32% and 58.75% respectively.

[0116] Example 16

[0117] The only difference from Example 1 is that the sulfonated oleic acid, dodecylamine, diesel and sodium lauryl sulfate in the collector are configured in a mass ratio of 4:6:1:1.

[0118] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains CaF2 83.06% and Li2O 0.88%, and the CaF2 and Li2O recovery rates are 76.83% and 62.53% respectively.

[0119] Example 17

[0120] The only difference from Example 1 is that the sulfonated oleic acid, dodecylamine, diesel and sodium lauryl sulfate in the collector are configured in a mass ratio of 20:2:1:1.

[0121] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 94.76% CaF2 and 0.82% Li2O, and the recovery rates of CaF2 and Li2O are 77.48% and 49.93% respectively.

[0122] Example 18

[0123] The only difference from Example 1 is that the sulfonated oleic acid, dodecylamine, diesel and sodium lauryl sulfate in the collector are configured in a mass ratio of 4:2:4:1.

[0124] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 93.34% CaF2 and 0.84% ​​Li2O, and the recovery rates of CaF2 and Li2O are 71.69% and 48.91% respectively.

[0125] Example 19

[0126] The only difference from Example 1 is that the sulfonated oleic acid, dodecylamine, diesel and sodium lauryl sulfate in the collector are configured in a mass ratio of 4:2:1:4.

[0127] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 92.45% CaF2 and 0.82% Li2O, and the recovery rates of CaF2 and Li2O are 72.97% and 49.13% respectively.

[0128] Example 20

[0129] The only difference from Example 1 is that the tannic acid, citric acid and lignin xanthate in the inhibitor are configured in a mass ratio of 10:10:1.

[0130] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 92.52% CaF2 and 0.94% Li2O, and the recovery rates of CaF2 and Li2O are 71.93% and 57.65% respectively.

[0131] Example 21

[0132] The only difference from Example 1 is that the tannic acid, citric acid and lignin xanthate in the inhibitor are configured in a mass ratio of 10:2:7.

[0133] After selecting fluorite lepidolite using the above method, after testing, the final closed-circuit test indicators obtained are: the fluorite lepidolite concentrate contains 93.34% CaF2 and 0.94% Li2O, and the recovery rates of CaF2 and Li2O are 72.59% and 58.17% respectively.

[0134] The results of the above examples show that the present invention overcomes the shortcomings of the prior art in which fluorite and lepidolite are separately recovered by flotation for a long time, there are many types of reagents, and the recovery rate is low, by improving the flotation reagents and processes. At the same time, the present invention overcomes the drawbacks of the use of water glass and acidified water glass, such as the difficulty in settling the tailings and acid corrosion, thereby achieving efficient recovery of fluorite and lepidolite resources in the tailings and improving the resource utilization of fluorite and lepidolite.

[0135] It should be noted that the present invention uses the above-described embodiments to illustrate the detailed structural features of the present invention. However, the present invention is not limited to these detailed structural features, and this does not mean that the present invention must rely on these detailed structural features to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacements for selected components, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

[0136] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the scope of protection of the present invention.

[0137] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0138] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A use of a collector for fluorite and lepidolite in tailings, characterized in that: The use includes using the collector to recover fluorite and lepidolite from tailings using a flotation process; The specific process includes the following: (1) adding the collector to the tailings slurry for rough separation to obtain fluorite and lepidolite coarse concentrate and tailings; the pH value of the tailings slurry is 10.5-12; (2) adding an inhibitor to the fluorite and lepidolite crude concentrate for beneficiation to obtain fluorite and lepidolite concentrate; The inhibitors are tannic acid, citric acid and lignin xanthate; The collector is composed of sulfonated oleic acid, fatty amine, diesel and sodium lauryl sulfate; The mass ratio of sulfonated oleic acid, fatty amine, diesel and sodium lauryl sulfate in the collector is (4-6):(2-3):1:1; The fatty amine includes one or a combination of at least two of laurylamine, octadecylamine or coconut amine.

2. The use according to claim 1, characterized in that The preparation method of the collector comprises the steps of mixing sulfonated oleic acid, fatty amine, diesel oil and sodium lauryl sulfate according to a formula.

3. The use according to claim 1, characterized in that In the tailings slurry of step (1), particles with a diameter of -0.074 mm account for 50-90% of the total solid particle mass.

4. The use according to claim 1, characterized in that The amount of collector added in the rough selection of step (1) is 200-800 g / t.

5. The use according to claim 1, characterized in that The rough selection in step (1) is performed at least once.

6. The use according to claim 1, characterized in that The tailings obtained in step (1) are scavenged at least once.

7. The use according to claim 6, characterized in that 50-100 g / t of collector is added during the sweeping.

8. The use according to claim 1, wherein The mass ratio of tannic acid, citric acid and lignin xanthate in the inhibitor of step (2) is (9-12):(1-3):

1.

9. The use according to claim 1, characterized in that The amount of inhibitor added in the concentration in step (2) is 180-650 g / t.

10. The use according to claim 1, characterized in that The selection in step (2) is performed at least 7 times.

11. The use according to claim 1, characterized in that When the selection in step (2) is performed for the first time, the amount of inhibitor added in the selection is 100-200 g / t.

12. The use according to claim 1, characterized in that When the selection in step (2) is performed for the second time, the amount of the inhibitor added is 70-150 g / t.

13. The use according to claim 1, characterized in that When the selection in step (2) is performed for the third time, the amount of the inhibitor added is 50-100 g / t.

14. The use according to claim 1, characterized in that When the selection in step (2) is performed for the fourth time, the amount of the inhibitor added is 30-70 g / t.

15. The use according to claim 1, characterized in that When the selection in step (2) is performed for the fifth time, the amount of the inhibitor added is 20-50 g / t.

16. The use according to claim 1, characterized in that When the selection in step (2) is performed for the sixth time, the amount of the inhibitor added is 10-30 g / t.

17. The use according to claim 1, characterized in that When the selection in step (2) is performed for the 7th time, the amount of the inhibitor added is 5-15 g / t.

18. The use according to claim 1, characterized in that The ore obtained from the concentration in step (2) is returned to the previous operation in sequence.

19. The use according to claim 1, wherein The use includes the following process: (1) adding the collector to the tailings slurry for rough separation to obtain fluorite and lepidolite coarse concentrate and tailings; (2) adding an inhibitor to the fluorite and lepidolite crude concentrate for beneficiation to obtain fluorite and lepidolite concentrate; The pH value of the tailings slurry in step (1) is 10.5-12; the particles of -0.074 mm in the tailings slurry account for 50-90% of the total solid particle mass; the amount of the collector added is 200-800 g / t; the roughing is performed at least once; the obtained tailings are scavenged at least once, and 50-100 g / t of the collector is added during the scavenging; The inhibitor in step (2) is tannic acid, citric acid and lignin xanthate, and the mass ratio of tannic acid, citric acid and lignin xanthate in the inhibitor is (9-12):(1-3):

1. The amount of the inhibitor added in the selection is 180-650 g / t; the selection is carried out at least 7 times, and the amount of the inhibitor added in the first selection is 100-200 g / t, and the amount of the inhibitor added in the second selection is 70-150 g / t. When the selection is carried out for the third time, the amount of the inhibitor added is 50-100 g / t, when the selection is carried out for the fourth time, the amount of the inhibitor added is 30-70 g / t, when the selection is carried out for the fifth time, the amount of the inhibitor added is 20-50 g / t, when the selection is carried out for the sixth time, the amount of the inhibitor added is 10-30 g / t, when the selection is carried out for the seventh time, the amount of the inhibitor added is 5-15 g / t, and the middlings obtained from the selection are sequentially returned to the previous operation.

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