Flotation method for lithium-containing porcelain clay ore

Abstract

The invention belongs to the field of flotation, and particularly relates to a lithium-containing china clay ore flotation method which comprises the following steps: carrying out flotation on to-be-separated minerals of lithium-containing china clay ore in a flotation reagent containing a collecting agent to obtain lithium china clay ore concentrate; the collecting agent is characterized in that the collecting agent is a compound shown in the formula 1 # imgabs0 #; and / or a product obtained by carrying out an addition reaction on a formula 2 (R-NH2) and a formula 3 # imgabs1 # in advance and then carrying out a saponification reaction with an alkali. According to the collecting agent for the lithium china clay ore, the component shown in the formula 1 is innovatively adopted as the collecting agent for the lithium china clay ore, in this way, on the basis of intermolecular coupling of beta-NH-and-COOM, the collecting agent can accidentally adapt to the surface characteristics of target minerals of the lithium china clay ore, high-selectivity collecting can be achieved, and effective collecting under the low-temperature and mild conditions can be achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral flotation, and in particular relates to a flotation method for lithium-containing china clay ore. Background Art

[0002] Lithium has the advantages of high specific heat, high electrical conductivity, and strong electrochemical activity. It is called "green high-energy metal" and "white oil" and is widely used in new energy, new materials and other fields. Under the background of the "dual carbon" strategic goal, my country's lithium battery new energy industry has developed rapidly and has become the world's largest lithium consumer, with its consumption accounting for about 40% of the world's original lithium resource output. Lithium is extracted mainly from lithium-containing kaolin, hard rock spodumene and salt lake brine, among which lithium-containing kaolin is an important component of ore extraction of lithium carbonate. Yichun, Jiangxi, known as the "Asian Lithium Capital", has rich lithium-containing kaolin resources. At present, the industry mainly uses the pre-de-sludge-flotation process to enrich and recover lithium mica concentrate.

[0003] The main collectors for flotation of lithium mica are cationic amine collectors and anionic fatty acid collectors. However, cationic amine collectors have problems such as high foam viscosity, poor fluidity, high freezing point, and sensitivity to ore mud. In addition, hydrochloric acid / acetic acid is generally required for configuration and dissolution. Acids are highly corrosive and volatile, and there are major safety hazards during storage, transportation and use. Although anionic collectors such as fatty acids have better selectivity, they are not resistant to low temperatures and require a large amount of reagents. Therefore, the amine cationic collectors and fatty acid anionic collectors that are currently used for flotation of lithium mica have obvious deficiencies. In order to solve the problems of existing collectors, researchers have gradually shifted from the research of single flotation collectors for lithium mica to the research of anionic-cationic composite collectors.

[0004] The Chinese patent document with publication number CN104741245A discloses that the use of dodecylamine or coconut amine in combination can achieve a lithium mica Li2O recovery rate of more than 90%, and the Li2O grade in the concentrate is more than 5.6%, which significantly improves the flotation recovery of lithium mica. The Chinese patent document with publication number CN111151381A discloses the use of N-isopropyl acrylamide (NIPAM) and N-[3-dimethylaminopropyl] methacrylamide (DMAPMA) two agents synergistically, and the use of combined collectors reduces the sensitivity of the agents to temperature. The Chinese patent document with publication number CN114160313A discloses the flotation of lithium mica ore by combining alkyl sulfonates, sodium oleate, alkyl polyamine ethers, polyoxyethylene sorbitan fatty acid esters, and tannins, which does not require pre-de-sludging and has high flotation efficiency. The Chinese patent document with publication number CN115970907A discloses an anionic-cationic collector compounded with primary amine, sodium hydroxide and oleic acid. The Chinese patent document with publication number CN116140069A discloses an anionic-cationic lepidolite collector compounded with sulfonic acid collector and amine collector, which is used for the flotation of fine-grained lepidolite ore.

[0005] Although the above-mentioned collectors have achieved certain effects, they need to be mixed and compounded in advance. The workers have high operating intensity, the reagent configuration operation is complicated, and the flotation index improvement is limited. There are also problems such as poor water solubility, low temperature intolerance, and weak collection performance. The collection capacity and selectivity of the reagents still have a lot of room for improvement. Summary of the invention

[0006] In view of the shortcomings of the prior art, the present invention aims to provide a flotation method for lithium-containing kaolin ore, aiming to improve the low-temperature capture capacity and capture selectivity of the lithium kaolin ore.

[0007] The mineral phases of different mineral types and the intercalation relationships between minerals are different, and the flotation scheme is difficult to simply transfer, and the flotation effect is difficult to transfer as expected. For example, for lithium kaolin ore, it belongs to lithium silicate ore, which is different from the conventional Li oxide ore and carbonate mineral phase, the gangue and gangue intercalation characteristics are different, and the flotation behavior is different. At present, the composition of the flotation collector of lithium kaolin ore is relatively complex, and the cost of the reagent is relatively high. In addition, it is difficult to adapt to the requirements of low-temperature flotation, and the low-temperature flotation performance is not ideal. In view of this problem, the present invention has been studied in depth and provides the following improvement scheme:

[0008] A flotation method for lithium-containing china clay ore, wherein the ore to be selected containing lithium china clay ore is floated in a flotation reagent containing a collector to obtain a lithium china clay ore concentrate; the collector is a compound of formula 1; and / or a product of formula 2 or formula 3 which is preliminarily subjected to an addition reaction and then subjected to a saponification reaction with an alkali;

[0009]

[0010] R-NH2 Formula 2

[0011]

[0012] The R is C 10 ~C 18 wherein M is H, K or Na; wherein R1 is Or *-CN; R2 is a C1~C4 alkyl group.

[0013] The present invention innovatively uses the component of formula 1 as a collector for lithium-containing kaolin ore. Based on the intermolecular coupling of -NH- and -COOM at the β position, it can unexpectedly adapt to the surface characteristics of the lithium kaolin ore and achieve highly selective capture. Moreover, it can also achieve effective capture under low temperature and mild conditions.

[0014] In the present invention, the lithium china clay ore includes at least one of lithium muscovite, lepidolite containing rubidium and cesium, ferrolithium mica, petalite and pyroxenite.

[0015] In Formula 1 of the present invention, R can be decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, or octadecyl; preferably, dodecyl, tetradecyl, hexadecyl, or octadecyl.

[0016] In the present invention, the collector can also be the reaction product. The molar ratio of Formula 2 to Formula 3 is 1:0.1-2.0; preferably 1:0.4-1. The present invention shows that under the preferred molar ratio, Formula 2 is in excess, and a composite collector comprising Formula 2 and Formula 1 can be obtained, which can be directly used for the flotation of lithium-containing china clay ore without separation, which can not only reduce the separation steps and components, but also unexpectedly improve the flotation effect of lithium-containing china clay ore.

[0017] In the present invention, the temperature of the addition reaction is 50 to 80°C, and the reaction time is preferably 30 to 60 minutes;

[0018] In the present invention, the alkali is at least one of sodium hydroxide and potassium hydroxide;

[0019] The molar ratio of formula 2 to the base is 1:0.1-2.0; preferably 1:0.5-1.5.

[0020] In the present invention, the saponification reaction temperature is 50 to 100° C., and the reaction time is preferably 10 to 40 minutes.

[0021] In the present invention, the collector comprises Formula 1 and Formula 2. Further, the molar ratio of Formula 1 to Formula 2 is 1:0.4-1.2. The present invention shows that the composite collector can further cooperate between molecules and further enhance the flotation effect of lithium-containing china clay ore.

[0022] In the present invention, the amount of the collector is 50 g / t or more, and in consideration of cost and effect, it may be further 200 to 600 g / t; further, it may be 250 to 450 g / t.

[0023] In the present invention, the pH value in the flotation stage is 5 to 9, and can further be 5.5 to 7.5.

[0024] In the present invention, the temperature in the flotation stage is below 35°C; further, it can be 10-25°C.

[0025] In the present invention, the flotation system also includes known flotation components such as inhibitors, frothers, and pH adjusters. The components can be well known in the industry, and the dosage of the components can be reasonably adjusted as needed. For example, the inhibitor can be sodium hexametaphosphate and other components, and its dosage can be 50-500 g / t; considering the cost and effect, it can be further 200-400 g / t.

[0026] Preferably, the lithium-containing china clay ore is a lithium-containing china clay ore with associated rubidium and cesium, and after flotation, the rubidium and cesium are enriched in the lithium china clay ore concentrate. The process described in the present invention can also realize the synchronous flotation utilization of the associated rubidium and cesium.

[0027] Beneficial effects:

[0028] (1) The collector of the present invention can achieve intramolecular synergy through the combination of β-NH- and -COOH groups. Both of them can act as mineralophilic groups and can react with metal particles on the surface of minerals, which can effectively improve the flotation recovery of target minerals in lithium-containing kaolin ore and improve the flotation grade and recovery rate of metals.

[0029] (2) The collector of the present invention has good water solubility and dispersibility. Compared with traditional collectors such as dodecylamine and coconut amine, it can be directly added to the flotation tank when used for mineral flotation, without the need to add acid (hazardous substances such as acetic acid, hydrochloric acid, sulfuric acid, etc.), thereby reducing equipment corrosion and environmental pollution. The agent is also safer and more environmentally friendly during addition and use.

[0030] (3) The collector of the present invention can be used under neutral flotation conditions and is insensitive to fine-particle ore mud. It can be directly used for the flotation of lithium-containing china clay ore without desludging. The foam fluidity is strong and it is suitable for the full-mud flotation process of lithium-containing china clay ore.

[0031] (4) The collector of the present invention is synthesized by a one-pot method, all raw materials are widely available, the synthesis process is simple, the reaction conditions are mild, the preparation process is green and environmentally friendly, and it is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is the infrared spectrum of Formula 1A prepared in Example 1;

[0033] Figure 2 is the infrared spectrum of Formula 1B prepared in Example 4;

[0034] Figure 3 Single mineral flotation flow chart provided for Examples 6 to 7;

[0035] Figure 4 This is a flotation flow chart of a lithium-containing china clay ore in Jiangxi Province that has not been desludged according to Example 8;

[0036] Figure 5 This is a flotation flow chart of a lithium-containing china clay ore after desludging in Jiangxi Province in Example 9;

[0037] Figure 6 This is a flotation flow chart of a lithium-containing china clay ore in Yichun, Jiangxi Province that has not been desludged, according to Example 10;

[0038] Figure 7 is the flotation froth diagram of Example 8 using Formula 1A;

[0039] Figure 8 This is the flotation froth diagram of Example 8 using traditional dodecylamine. DETAILED DESCRIPTION

[0040] In order to make the technical problems, technical solutions and advantages to be solved by the present invention more clear, they will be described in detail below with reference to the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0041] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0042] In the present invention, as an optional scheme, the collector of Formula 1 is exemplified by Formula 1A and Formula 1B.

[0043]

[0044] The present invention also provides a method for preparing the collector, comprising the following two steps:

[0045] Step (1): Formula 2 (R-NH2) and Formula 3 (Formula 3A Formula 3B ) mixing and stirring to carry out addition reaction at a certain temperature;

[0046] Step (2): subjecting the addition product to a saponification reaction with an aqueous solution of hydroxide at a certain temperature to obtain a collector;

[0047] The base is an alkali metal hydroxide, preferably at least one of sodium hydroxide and potassium hydroxide;

[0048] Preferably, the ratio of the amount of the substance of Formula 2, Formula 3 and the base is 1:0.1-2.0:0.1-2.0, and the amount of solvent water is 1-100 ml water / mol alkali metal hydroxide.

[0049] Preferably, the esterification reaction temperature of step (1) is 50-80°C, and the reaction time is 30-60 min; the saponification reaction temperature of step (2) is 50-100°C, and the reaction time is 10-40 min.

[0050] The technical solution of the present invention can realize one-pot preparation.

[0051] The invention also provides an application of the collector, which is used as a flotation collector for minerals.

[0052] The present invention has found that the compound of formula I is used as a collector for lithium-containing china clay ores to obtain excellent collection ability and selectivity for the target mineral.

[0053] Preferably, the lithium-containing china clay ore is one or more of lithium muscovite, rubidium-cesium-containing lithium mica, iron lithium mica, petalite, and pyrophyllite.

[0054] The flotation process of the present invention is as follows: a) crushing and grinding the ore before flotation; b) adding flotation reagents to adjust the slurry during grinding or flotation, wherein the added reagents contain at least one collector of the present invention; c) floating out useful metal minerals through froth flotation.

[0055] In the present invention, during the flotation stage, the pH of the slurry is 2-12, preferably 5-9.

[0056] Preferably, the dosage of the collector is 50-500 g / t based on the mass of the flotation feed ore.

[0057] The present invention also provides a flotation agent for lithium-containing china clay ore, comprising the collector (compound of formula I).

[0058] The flotation reagents may also contain other reagents known in the industry, such as dodecylamine, etheramine, coconut amine, oleic acid (salt), dodecyl sulfate, dodecyl (benzene) sulfonate, oxidized paraffin soap, alkyl (ether) alcohols, etc. The reagents may be ingredients known in the industry, and the amount added may also be adjusted based on existing means.

[0059] In the present invention, the pH of the pulp in the flotation stage has a reasonable operating error of ±0.1. The temperature in the flotation stage also has an operating error of plus or minus 2°C.

[0060] Example 1

[0061] Preparation of Collector of Formula 1A:

[0062] 18.52 parts of dodecylamine were placed in a reaction bottle and stirred, and then methyl acrylate (1 eqv) was added, and the temperature was raised to 60°C and stirred for 30 minutes, and then sodium hydroxide (1 eqv) solution was added, and the temperature was raised to 80°C and stirred for 10 minutes. The reaction generated a white colloidal substance, and the product was cooled to room temperature to form a white waxy solid. After constant temperature drying, Formula 1A was obtained. The obtained product was characterized by infrared spectroscopy. The infrared spectrum is shown in Figure 1 , infrared spectrum analysis is shown in Table 1.

[0063] Table 1 Infrared spectrum analysis of surfactant of formula 1A

[0064]

[0065] Example 2

[0066] 37.82 parts of dodecylamine were placed in a reaction bottle and stirred, and then methyl acrylate (0.5 eqv) was added, the temperature was raised to 70°C and stirred for reaction for 40 min, and then sodium hydroxide (0.5 eqv) solution was added, the temperature was raised to 85°C and stirred for 20 min, and the reaction generated a white colloidal substance, which was cooled to room temperature and the product was a white waxy solid, thereby obtaining an addition product comprising Formula 1A and dodecylamine.

[0067] Example 3

[0068] 37.82 parts of dodecylamine were placed in a reaction bottle and stirred, and then methyl acrylate (1 eqv) was added, and the temperature was raised to 80°C and stirred for reaction for 45 min. Then a solution of sodium hydroxide (0.5 eqv) was added, and the temperature was raised to 90°C and stirred for 30 min. The reaction generated a white colloidal substance, which was cooled to room temperature and the product was a white waxy solid. After constant temperature drying, the product of formula 1A was obtained.

[0069] Example 4

[0070] Preparation of Collector of Formula 1B:

[0071] 29.85 parts of octadecylamine were placed in a reaction bottle and stirred, and then 8.74 parts of methyl acrylate were added, and the temperature was raised to 85°C and stirred for 45 minutes, and then a sodium hydroxide solution (wherein the weight of sodium hydroxide was 4.26 parts) was added, and the temperature was raised to 85°C and stirred for 30 minutes. The reaction generated a white colloidal substance, and the product was cooled to room temperature to be a white waxy solid. After constant temperature drying, Formula 1B was obtained. The obtained product was characterized by infrared spectroscopy structure, and the infrared spectrum is shown in Figure 2 , infrared spectrum analysis is shown in Table 2.

[0072] Table 2 Infrared spectrum analysis of surfactant of formula 1B

[0073]

[0074] Example 5

[0075] 59.89 parts of octadecylamine were placed in a reaction bottle and stirred, and then 17.48 parts of methyl acrylate were added, the temperature was raised to 80°C and stirred for reaction for 40 minutes, and then 8.34 parts of sodium hydroxide solution were added, the temperature was raised to 90°C and stirred for 30 minutes, and the reaction generated a white colloidal substance, which was cooled to room temperature and the product was a white waxy solid, to obtain a product of formula 1B.

[0076] Example 6

[0077] Flotation performance of formula 1A on lepidolite under different dosage conditions:

[0078] Use Figure 3 The process shown is to flotate lepidolite, wherein the collector is Formula 1A, the stirring speed of the flotation machine is 1650r / min, the pulp pH is 7.0, and the lepidolite with a particle size of 0.038-0.074mm is floated for 4min (flotation temperature is 20°C). When the concentration of the collector of Formula 1A is 20mg / L, the flotation recovery rate of lepidolite is 56.39%; when the concentration of the collector is 80mg / L, the flotation recovery rate of lepidolite is 81.67%; when the concentration of the collector is 100mg / L, the flotation recovery rate of lepidolite is 89.08%.

[0079] Flotation performance of dodecylamine on lepidolite under different dosage conditions:

[0080] Use Figure 3The process shown is for flotation of lepidolite, wherein the collector is dodecylamine, and other conditions are the same, for example, when the stirring speed of the flotation machine is 1650r / min, the pH of the ore pulp is 7.0, and the lepidolite with a particle size of 0.038-0.074mm is floated for 4min (the flotation temperature is 20°C). When the concentration of the dodecylamine collector is 20mg / L, the flotation recovery rate of the lepidolite is only 22.17%; when the concentration of the collector is 80mg / L, the flotation recovery rate of the lepidolite is only 28.05%; when the concentration of the collector is 100mg / L, the flotation recovery rate of the lepidolite is 74.45%.

[0081] It can be seen that under different dosage conditions, compared with traditional dodecylamine, the flotation recovery rate of lithium mica in Example 1 of the present invention is significantly higher than that of dodecylamine, showing a stronger collection ability.

[0082] Example 7

[0083] Flotation performance of lepidolite according to formula 1A under different pH conditions:

[0084] Use Figure 3 The process shown in the figure is used to float lepidolite. The collector is the addition product prepared in Example 2. Hydrochloric acid and sodium hydroxide solution are used as slurry pH adjusters. Lepidolite with a flotation particle size of 0.038 to 0.074 mm (flotation temperature is 20° C.) is floated. When the collector concentration is 100 mg / L, at a pH of 5.5, the recovery rate of lepidolite is 95.37%; at a pH of 7.0, the recovery rate of lepidolite is 94.06%.

[0085] Flotation performance of dodecylamine on lepidolite under different pH conditions:

[0086] Use Figure 3 The process shown in the figure is used to float lithium mica, with dodecylamine as the collector, hydrochloric acid and sodium hydroxide solution as the pulp pH adjusters, and lithium mica with a flotation particle size of 0.038 to 0.074 mm (flotation temperature is 20° C.). When the collector concentration is 100 mg / L and the pH is 5.5, the recovery rate of lithium mica is 91.50%; when the pH is 7.0, the recovery rate of lithium mica is 88.31%.

[0087] It can be seen that under different pH conditions, compared with traditional dodecylamine, the flotation recovery rate of lepidolite in Example 1 of the present invention is higher than that of dodecylamine, showing better capture ability.

[0088] Example 8

[0089] The flotation application of the embodiment of the present invention in a lithium-containing porcelain clay mine in Jiangxi Province without desludging:

[0090] A lithium-containing porcelain clay ore in Jiangxi Province that has not been desludged has a Li2O grade of 0.28%, a Rb2O grade of 0.28%, and a Cs2O grade of 0.032%. Figure 4 The process flow shown in the figure is used to flotate the lithium-containing china clay ore. The grinding fineness is -0.074mm, accounting for 70%. Sodium hexametaphosphate (300g / t) is used as an inhibitor. The pH of the ore pulp is about 7.0 and the temperature is 15°C. The specific process flow and flotation reagent system are shown in Figure 4 The flotation results are shown in Table 1. From the results, it can be seen that the metal grade and recovery rate of the concentrate obtained by using the collector of the embodiment of the present invention are higher. Among them, compared with the traditional dodecylamine, the recovery rates of Li2O, Rb2O and Cs2O in the concentrate of the embodiment 1 of the present invention are increased by 24.75, 13.24 and 19.51 percentage points respectively; compared with the traditional dodecylamine, the recovery rates of Li2O, Rb2O and Cs2O in the concentrate of the embodiment 2 of the present invention are increased by 26.95, 16.29 and 25.16 percentage points respectively. The above results show that the collector of the embodiment of the present invention has a stronger capture ability and selectivity for lithium-containing china clay ore, can be directly used for the flotation of lithium-containing china clay ore without desludging, and is suitable for the full mud flotation process of lithium-containing china clay ore.

[0091] Table 1 Flotation test results of the present invention in a lithium-containing porcelain clay ore in Jiangxi Province without desludging

[0092]

[0093] Example 9

[0094] The flotation application of the collector of the embodiment of the present invention in a lithium-containing porcelain clay mine after desludging in Jiangxi:

[0095] Use Figure 5 The process flow shown in the figure is used to flotate a lithium-containing porcelain clay ore after desludging in Jiangxi. The grinding fineness is -0.074mm, accounting for 70%. Sodium hexametaphosphate (300g / t) is used as an inhibitor. The pH of the ore pulp is about 7.0 and the temperature is 15℃. The specific process flow and flotation reagent system are shown in Figure 5 The flotation results are shown in Table 2. From the results, it can be seen that the recovery rates of Li2O, Rb2O and Cs2O in the concentrate using the collector of Example 1 of the present invention are equivalent to those using dodecylamine, but the grades of Li2O, Rb2O and Cs2O in the concentrate are increased by 0.19, 0.06 and 0.019 percentage points respectively; using the collector of Example 2 of the present invention, compared with the use of dodecylamine, the grades and recovery rates of Li2O, Rb2O and Cs2O in the concentrate are significantly improved, among which the metal grades are increased by 0.16, 0.02 and 0.014 percentage points respectively, and the recovery rates are increased by 12.98, 4.20 and 4.57 percentage points respectively. The above results show that the collector of the embodiment of the present invention has better capture ability and selectivity for lithium-containing china clay ore.

[0096] Table 2 Flotation test results of the present invention in a desludging lithium-containing porcelain clay ore in Jiangxi

[0097]

[0098] Example 10

[0099] The flotation application of the collector of the embodiment of the present invention in a lithium-containing porcelain clay mine in Yichun, Jiangxi Province without desludging:

[0100] A lithium-containing porcelain clay mine in Yichun, Jiangxi Province, which has not been desludged, has a Li2O grade of 0.52%, a Rb2O grade of 0.18%, and a Cs2O grade of 0.04%. Figure 6 The process flow shown in the figure is used to flotate the lithium-containing china clay ore. The grinding fineness is -0.074mm, accounting for 65%. Sodium hexametaphosphate (300g / t) is used as an inhibitor. The pH of the ore pulp is about 7.0 and the temperature is 15°C. The specific process flow and flotation reagent system are shown in Figure 6 The flotation results are shown in Table 3. From the results, it can be seen that the metal grade and recovery rate of the concentrate obtained by using the collector of the embodiment of the present invention are higher. Among them, compared with the traditional dodecylamine, the grades of Li2O, Rb2O and Cs2O in the concentrate of the invention embodiment 1 are increased by 0.48, 0.12 and 0.034 percentage points, respectively, and the recovery rate is increased by 10.94, 6.59 and 9.60 percentage points, respectively; compared with the traditional dodecylamine, the recovery rates of Li2O, Rb2O and Cs2O in the concentrate of the invention embodiment 2 are increased by 6.17, 3.03 and 5.56 percentage points, respectively. The above results show that the collector of the embodiment of the present invention has a stronger capture ability and selectivity for lithium-containing china clay ore, and is also suitable for the full mud flotation process of lithium-containing china clay ore.

[0101] Table 3 Flotation test results of the present invention in a lithium-containing porcelain clay ore in Yichun, Jiangxi Province without desludging

[0102]

[0103] In summary, the collector described in the present invention has excellent collecting ability and can obtain excellent collecting effect under mild and low temperature conditions.

[0104] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A flotation method for lithium-containing china clay ore, wherein the ore to be selected containing lithium china clay ore is floated in a flotation agent containing a collector to obtain a lithium china clay ore concentrate; characterized in that: The collector is a compound of formula 1; and / or a product of formula 2 or formula 3 which is pre-addition-reacted and then subjected to saponification reaction with a base; R-NH2 Formula 2 The R is C 10 ~C 18 wherein M is H, K or Na; wherein R1 is Or *-CN; R2 is a C1~C4 alkyl group.

2. The flotation method of lithium-containing china clay ore according to claim 1, characterized in that: The lithium china clay ore comprises at least one of lithium muscovite, lepidolite containing rubidium and cesium, ferrolithium mica, petalite and pyroxenite.

3. The flotation method of lithium-containing china clay ore according to claim 1, characterized in that: The molar ratio of Formula 2 to Formula 3 is 1:0.1-2.0; preferably 1:0.4-1.

4. The flotation method of lithium-containing china clay ore according to claim 1, characterized in that: The temperature of the addition reaction is 50 to 80° C., and the reaction time is preferably 30 to 60 min.

5. The flotation method of lithium-containing china clay ore according to claim 1, characterized in that: The alkali is at least one of sodium hydroxide and potassium hydroxide; The molar ratio of formula 2 to the base is 1:0.1-2.0; preferably 1:0.5-1.

5.

6. The flotation method of lithium-containing china clay ore according to claim 5, characterized in that: The saponification reaction temperature is 50 to 100° C., and the reaction time is preferably 10 to 40 minutes.

7. The flotation method of lithium-containing china clay ore according to any one of claims 1 to 6, characterized in that: The collector comprises formula 1 and formula 2; Preferably, the molar ratio of Formula 1 to Formula 2 is 1:0.4-1.

2.

8. The flotation method of lithium-containing china clay ore according to any one of claims 1 to 6, characterized in that: The amount of the collector used is 50 g / t or more, and can be further 200-600 g / t in consideration of cost and effect; further can be 250-450 g / t.

9. The flotation method of lithium-containing china clay ore according to any one of claims 1 to 6, characterized in that: The pH value in the flotation stage is 5 to 9; preferably 5.5 to 7.

5.

10. The flotation method of lithium-containing china clay ore according to any one of claims 1 to 6, characterized in that: The temperature in the flotation stage is below 35°C, preferably 10 to 25°C; Preferably, the lithium-containing kaolin ore is a lithium-containing kaolin ore co-existing with rubidium and cesium, and after flotation, the rubidium and cesium are enriched in the lithium kaolin ore concentrate.

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