A depressant-free flotation method for fluorite beneficiation

Abstract

This invention discloses a depressant-free flotation method for fluorite beneficiation. The method specifically includes the following steps: Step 1: After grinding, the fluorite ore is added to a flotation cell along with an appropriate amount of water. The mixture is stirred and homogenized in the flotation machine to obtain a fluorite slurry. Step 2: A certain amount of collector is added to the fluorite slurry from Step 1, and stirring is continued for 1-5 minutes. Then, a certain amount of frother is added to adjust the slurry. The collector is a BHA-Ce mixture. Step 3: Aeration is performed, and flotation frothing is carried out to obtain fluorite rough concentrate and tailings. This invention uses a mixture of benzoyl hydroxyxamic acid and cerium trichloride as a highly efficient collector for fluorite flotation, directly eliminating the need for depressants. This invention has no special requirements for the flotation environment and can reduce the cost of flotation reagents, subsequent tailings wastewater treatment, and environmental protection.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of mineral separation, and particularly relates to a beneficiation method for fluorite without using inhibitors. BACKGROUND

[0002] Fluorite is mainly composed of calcium fluoride CaF2, which is the main source of fluorine in industry. Fluorite ore is usually closely associated with gangue minerals such as quartz, calcite, dolomite, barite, and kaolinite. Because the magnetic properties and densities of fluorite and these gangue minerals are less different, the separation effect of fluorite by magnetic separation and gravity separation is not good, so the flotation method is generally used as the main method for separating fluorite in industry. The flotation process of fluorite varies in the flotation reagent system according to the different types and contents of gangue in the raw ore. Generally, the flotation of fluorite is carried out in an alkaline environment, so the commonly used pH adjuster is mainly sodium hydroxide, sodium carbonate, and sodium bicarbonate, etc. The collectors for fluorite include anionic oxygen-containing acid, cationic amine, and ion-variable amphiphilic collectors, etc. The most common anionic collectors are fatty acids and oleic acids, etc. These surfactants contain carboxylic acid, sulfonic acid, etc. groups, which can react with the calcium points on the surface of fluorite to adsorb and collect. They can be used for the flotation separation of fluorite and gangue minerals such as quartz, calcite, dolomite, and barite, but must be used with corresponding gangue inhibitors. For example, when sodium oleate or oxidized paraffin soap is used to float fluorite and quartz, acidified water glass is generally used as the inhibitor for quartz (Chinese patent 202110802638.7, a fluorite ore beneficiation method, Wu Yanni; Chinese patent CN202210687338.3, a beneficiation method for fluorite ore, Li Yan); when oleic acid or fatty acid is used to separate fluorite and calcite or dolomite, humic acid, tannic acid, and other organic acids are used as the inhibitors for calcite and dolomite (for example, Chinese patent, a beneficiation method for high-carbonate fluorite, published patent number CN107377198B; Chinese patent, a beneficiation method for high-carbonate fluorite ore, published patent number CN103706485B; Chinese patent, an inhibitor for high-calcium fluorite ore and a flotation method, Wang Xu, published patent number CN115814957A). The most common cationic amine collectors are octadecylamine, dodecylamine, mixed amine, and coconut amine, etc. This type of collector is usually used as a gangue collector for reverse flotation when separating fluorite and gangue minerals, so as to preferentially float some gangue minerals in the raw ore, so as to separate fluorite from the tailings in subsequent operations. However, even if a cationic collector is used, the use of an inhibitor is still unavoidable (for example, Chinese patent CN202211402084.2, application of an inhibitor in fluorite reverse flotation for removing calcite, Wang Xun). Therefore, the current fluorite flotation process cannot avoid the use of inhibitors.

[0003] In the existing fluorite flotation process, due to the limited selectivity of various collectors, it is impossible to only adsorb on fluorite without adsorbing on other gangue minerals, which is the main reason for the inevitable use of depressants in flotation. The use of depressants not only directly increases the cost of mineral processing, but also brings various problems to the subsequent treatment work, among which increasing the difficulty of tailings wastewater treatment and polluting the environment are common problems. Although the selection of depressants is mostly organic acids when selecting reagents, and it is tried not to use reagents that are harmful to the environment, but organic acids will still pollute the water body after entering the water body, so they still cannot be directly discharged without treatment. On the other hand, water glass (sodium silicate) is the main depressant for depressing silicate gangue minerals such as quartz, and large-scale use can easily cause the viscosity of tailings water to increase and not easy to settle, bringing many inconveniences to wastewater treatment and increasing the cost of treatment. Therefore, to solve the series of mineral processing problems caused by flotation depressants, the best solution is not to use depressants.

[0004] Based on the above reasons, the present application aims to provide a mineral processing method for flotation of fluorite without depressant, which can effectively float fluorite from fluorite ore without adding a large amount of depressant and is environmentally friendly. SUMMARY

[0005] Based on the above reasons, in view of the problems or defects in the prior art, the purpose of the present application is to provide a mineral processing method for flotation of fluorite without depressant, which solves or at least partially solves the above technical defects in the prior art.

[0006] In order to achieve the above first purpose of the present application, the technical scheme adopted by the present application is as follows:

[0007] A mineral processing method for flotation of fluorite without depressant, the method specifically comprises the following steps:

[0008] Step one: after grinding the fluorite ore, it is added to the flotation tank, and an appropriate amount of water is added, and stirring is carried out in the flotation machine, and mixing is obtained to obtain fluorite slurry;

[0009] Step two: a certain amount of collector is added to the fluorite slurry in step one, and stirring is continued for 1-5 min; then a certain amount of foaming agent is added to adjust the slurry; wherein: the collector is a BHA-Ce mixture;

[0010] Step three: air charging, carrying out flotation and scraping bubble operation, obtaining fluorite rough concentrate and tailings.

[0011] Specifically, in the above technical scheme, the fluorite ore can be ordinary fluorite or high-calcium fluorite, and the mineral processing method described above has better separation effect on ordinary fluorite than on high-calcium fluorite.

[0012] Specifically, the BHA-Ce mixture represents a mixture of an organic substance benzylhydroxylamine (BHA) and metal Ce ions.

[0013] Specifically, the above technical solution, the grinding is specifically to grind the fluorite raw ore to the particle size at which fluorite and other gangue minerals are dissociated. Since the grinding fineness will have a large floating range due to the different properties of the raw ore, different ore properties are different, and the particle size required by grinding is also different, for example, the grinding fineness can be-0.074 mm particle size accounting for 50-95%.

[0014] Further, in the above technical solution, the amount of the collector is 100-1000 g / t, that is, the amount of the collector required for processing 1 ton of fluorite raw ore is 100-1000 g.

[0015] Further, in the above technical solution, the amount of the collector is preferably 500 g / t, that is, the amount of the collector required for processing 1 ton of fluorite raw ore is preferably 500 g.

[0016] Further, in the above technical solution, the BHA-Ce mixture is prepared by the following steps:

[0017] According to the proportion, benzylhydroxylamine (BHA) and cerium trichloride (CeCl3) are sequentially added to deionized water, stirred and mixed to obtain the BHA-Ce mixture. The BHA-Ce mixture can be appropriately changed in concentration according to the flotation reagent system or process requirements and used as a flotation collector.

[0018] Further, in the above technical solution, the mass ratio of cerium trichloride to benzylhydroxylamine is 1:30-1:20. If the amount of cerium trichloride is too large, it will directly form a precipitate with BHA, which is equivalent to consuming BHA and cannot play a collecting role.

[0019] Further, in the above technical solution, the stirring time can not be specifically limited, as long as the uniform mixing and dissolution of benzylhydroxylamine and cerium trichloride in water can be achieved. For example, the stirring time can be 30 min.

[0020] Preferably, in the above technical solution, the mass ratio of cerium trichloride to benzylhydroxylamine is 1:30.

[0021] Further, in the above technical solution, the frother is any one of pinol oil or methyl isobutyl carbinol (MIBC).

[0022] Further, in the above technical solution, the amount of the frother is 20-80 g / t, that is, the amount of the frother required in 1 ton of fluorite raw ore is 20-80 g.

[0023] Furthermore, in the above technical solution, the preferred amount of foaming agent is 50g / ton, that is, the preferred amount of foaming agent required in 1 ton of fluorite ore is 50g.

[0024] Furthermore, in the above technical solution, the flotation skimming time is 5 to 20 minutes, preferably 10 minutes.

[0025] This invention provides a mineral processing method for fluorite flotation that uses a mixture of the organic compound benzo[a]hydroxyxamic acid (BHA) and metallic Ce ions as a collector, without the use of depressants. This collector primarily reacts with benzo[a]hydroxyxamic acid (BHA) and metallic Ce ions (Ce ions) through the flotation process. 3+ This mixture of soluble metal salts is used as a collector. Due to its strong selective collection effect on fluorite, this mixed collector has almost no collection effect on common gangue minerals such as quartz, calcite, and dolomite. This is mainly because cerium ions can selectively adsorb onto fluorine particles on the fluorite surface but not onto the gangue mineral surface. When BHA is mixed with cerium ions, a BHA-Ce complex is formed, which has a good selective collection effect on fluorite. Therefore, fluorite can be directly floated without the use of gangue inhibitors during the separation process.

[0026] A comparison of the fluorite flotation process provided by this invention with the conventional process is shown in the appendix. Figure 1 .from Figure 1 As can be seen, the inhibitor-free flotation process is largely unchanged from the conventional fluorite flotation process, directly omitting the inhibitor usage step. Furthermore, this invention's inhibitor-free flotation process has more lenient requirements on the pH conditions of the flotation pulp. Under natural conditions, the pH of the flotation pulp is not lower than 6, allowing the collector to be added directly for flotation. This is mainly because BHA can exert its collecting effect within a pH range of 6-8, causing the adsorbed minerals to float hydrophobically. The natural pH of fluorite ore in the pulp is typically between 6 and 7, which is the range within which BHA can function effectively as a collector. On the other hand, excessively high pH values ​​(pH>8) are detrimental to the effectiveness of the BHA-Ce mixture because when the hydroxide content in the pulp is too high, cerium ions preferentially react with hydroxide ions to form cerium hydroxide (Ce(OH)3) precipitate, causing the cerium ions to lose their selective adsorption effect on fluorite.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] This invention addresses the problems of high beneficiation costs, difficult tailings wastewater treatment, and environmental issues associated with the use of large amounts of depressants in existing fluorite flotation techniques. It proposes an effective solution: a mixture of benzo[a]hydroxyxamic acid and cerium trichloride is used as a highly efficient collector for fluorite flotation, eliminating the need for depressants. This invention requires no special environmental conditions for flotation and reduces costs associated with flotation reagents, tailings wastewater treatment, and environmental protection. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, the drawings in the following description only constitute some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained without creative effort based on these drawings.

[0030] Figure 1 Fig. A and Fig. B are a conventional fluorite flotation process flow chart and a fluorite flotation process flow chart without depressant, respectively;

[0031] Figure 2 Fig. A and Fig. B are a conventional fluorite flotation process flow chart and a fluorite flotation process flow chart without depressant, respectively;

[0032] Figure 3 Fig. A and Fig. B are a conventional fluorite flotation process flow chart and a fluorite flotation process flow chart without depressant, respectively;

[0033] Figure 4 Fig. A and Fig. B are a conventional fluorite flotation process flow chart and a fluorite flotation process flow chart without depressant, respectively;

[0034] Figure 5 Fig. A and Fig. B are a conventional fluorite flotation process flow chart and a fluorite flotation process flow chart without depressant, respectively. DETAILED DESCRIPTION

[0035] The present application will be further described in detail through the following implementation cases. The implementation cases are implemented on the premise of the present application technology, and the detailed implementation mode and specific operation process are given to illustrate the creativity of the present application, but the protection scope of the present application is not limited to the following implementation cases.

[0036] According to the information contained in the present application, various changes can be easily made to the precise description of the present application by those skilled in the art. It should be understood that the scope of the present application is not limited to the defined processes, properties or components, as these embodiments and other descriptions are only illustrative of the specific aspects of the present application.

[0037] In order to better understand the present application without limiting the scope of the present application, all the numbers and other numerical values used in the present application to express the amount, percentage, and other values should be understood as being modified by the word "about" in all cases. Therefore, unless specifically stated otherwise, the numerical parameters set forth in the specification are approximations that can vary depending on the desired properties sought to be obtained by varying the properties. Each numerical parameter should be considered as being at least ascribed to the reported significant digits and to the normal rounding off method.

[0038] The equipment and raw materials used in the present application can be purchased from the market or are commonly used in the art. The methods in the following examples are conventional methods in the art unless otherwise specified.

[0039] Example 1

[0040] Comparison of high-calcium fluorite ore flotation with no depressant using BHA-Ce mixed collector with conventional process.

[0041] The high-calcium fluorite ore sample used in this example is a certain calcite-type high-calcium fluorite ore sample from Sichuan, China, in which the proportion of calcite (calcium carbonate CaCO3) is as high as 32.8%, and the fluorite grade is only about 8%. The main component analysis of the raw ore sample is shown in Table 1. The conventional beneficiation process flow of the raw ore is shown in Figure 2 , and the process flow of the no-depressant flotation is shown in Figure 3 .

[0042] After the raw ore is ground to a particle size of -0.074 mm accounting for 88%, first, the pH adjusting agent sodium bicarbonate is added and stirred for 3 minutes to adjust the pH of the ore slurry to about 7.5. In the no-depressant process, the pH is not adjusted, and the natural pH condition is maintained, with pH = 6-7. Then, in the conventional flotation process, the gangue depressants acidified water glass and sodium humate are added and stirred for 5 minutes, and in the no-depressant process, no depressant is added. Next, in the conventional flotation process, the collector is added and stirred for 3 minutes without adding a frother, and in the no-depressant process, the collector is added and then the frother pine oil is added. Finally, both processes are aerated to start flotation, and the flotation time is 10 minutes. After flotation is completed, the foam product, i.e., the fluorite rough concentrate product, and the ore slurry sediment, i.e., the tailings product, are obtained. In this example, oleic acid is used as the fluorite roughing collector in the conventional flotation process, and BHA-Ce mixture is used as the fluorite roughing collector in the no-depressant flotation process. Among them:

[0043] The dosage of oleic acid is 50 grams per ton (i.e., the dosage of oleic acid required for processing 1 ton of high-calcium fluorite ore is 50 grams), and the dosage of BHA-Ce mixture is 220 grams per ton (i.e., the dosage of BHA-Ce mixture required for processing 1 ton of high-calcium fluorite ore is 220 grams). In the conventional flotation process, the dosage of the depressants includes 3700 grams per ton of acidified water glass (i.e., the dosage of acidified water glass required for processing 1 ton of high-calcium fluorite ore is 3700 grams) and 450 grams per ton of sodium humate (i.e., the dosage of sodium humate required for processing 1 ton of high-calcium fluorite ore is 450 grams). The dosage of the frother pine oil is 50 grams per ton (i.e., the dosage of pine oil required for processing 1 ton of high-calcium fluorite ore is 50 grams). The flotation tests are carried out respectively, and the results are compared in Table 2.

[0044] Among them: the above-mentioned acidified water glass is prepared by mixing 1500 g of sulfuric acid with 2200 g of water glass (sodium silicate) and stirring uniformly.

[0045] The BHA-Ce mixture is prepared by the following steps:

[0046] The BHA and CeCl3 are added into the deionized water in the proportion, and stirred to obtain the BHA-Ce mixture; the mass ratio of the CeCl3 to the BHA is 1:30.

[0047] The oleic acid in the conventional flotation process can play a foaming role.

[0048] The data in Table 1 are obtained by XRF fluorescence semi-quantitative analysis or chemical analysis method, and the analysis results are from the detection institutions with detection and analysis qualification.

[0049] Table 1 Analysis of main components of raw ore samples

[0050] Ingredients SiO2 Al2O3 CaCO3 MgO [K2O] Na2O CaF2 Content, % 17.61 20.54 32.8 11.27 0.79 3.48 8.00 Ingredients BaO S Fe As Content, % 1.10 0.004 0.42 0.01

[0051] The grade results of the raw ore and the crude fluorite concentrate in Table 2 are obtained by chemical analysis of the detection institutions with detection and analysis qualification, and the recovery rate of the tailings and all products is calculated according to the recovery rate calculation formula 1:

[0052] The CaF2 grade of the raw ore = (the CaF2 grade of the crude concentrate x the crude concentrate yield + the CaF2 grade of the tailings x the tailings yield) / the raw ore yield x 100%;

[0053] The CaF2 recovery rate of the crude concentrate = (the CaF2 grade of the crude concentrate x the crude concentrate yield) / (the CaF2 grade of the raw ore x the raw ore yield) x 100%;

[0054] The CaF2 recovery rate of the tailings = (1-the CaF2 recovery rate of the crude concentrate) x 100%.

[0055] Table 2 Flotation test results

[0056]

[0057] The results show that compared with the conventional process, the CaF2 grade of the crude concentrate can be improved by using the non-inhibitor process, while the recovery rate is similar to that of the conventional process, and the enrichment ratio of fluorite in the crude concentrate is higher.

[0058] However, due to the absence of inhibitors, the flotation reagent cost will be greatly saved. Table 3 is a comparison of the reagent costs of the two flotation processes according to the market price. As shown in Table 3, the non-inhibitor process can save about 13% in reagent cost compared with the conventional process. The subsequent tailings wastewater treatment cost is not included in the calculation.

[0059] Table 3 Comparison of flotation reagent costs of two processes

[0060]

[0061] Example 2

[0062] Comparison of high-calcium fluorite ore flotation with BHA-Ce mixed collector without depressant and conventional process.

[0063] The high-calcium fluorite ore sample is a certain dolomite-type high-calcium fluorite ore sample in Inner Mongolia, in which the proportion of dolomite and calcite (calcium carbonate CaCO3) is as high as 50%, and the fluorite grade is about 32%. The main component analysis of the raw ore sample is shown in Table 4. The conventional beneficiation process flow of the raw ore in this embodiment is shown in Figure 4 , and the depressant-free flotation process flow of this embodiment is shown in Figure 5 .

[0064] After the raw ore is ground to 92% of the -0.074 mm particle size, the conventional process first adds the pH adjuster sodium hydroxide and stirs for 3 minutes to adjust the pH of the ore slurry to about 7.5, and the depressant-free process uses the natural condition with pH = 7. Then the conventional process sequentially adds the gangue depressants acidified water glass, sodium humate, and tannic acid and stirs for 5 minutes, and the depressant-free process does not add depressants. Next, the conventional flotation process adds the collector and stirs for 3 minutes without adding a foaming agent, and the depressant-free process adds the collector and then adds the foaming agent pine oil. Finally, both processes are aerated to start flotation, and the flotation time is 10 minutes. After flotation, the foam product, i.e., the fluorite rough concentrate product, and the ore slurry sediment, i.e., the tailings product, are obtained.

[0065] In this embodiment, sodium oleate is used as the fluorite roughing collector in the conventional process, and BHA-Ce mixture is used as the fluorite roughing collector in the depressant-free process. The dosage of sodium oleate is 65 g / t (i.e., the dosage of sodium oleate required for processing 1 ton of high-calcium fluorite ore is 65 g), and the dosage of BHA-Ce mixture is 500 g / t (i.e., the dosage of BHA-Ce mixture required for processing 1 ton of high-calcium fluorite ore is 500 g). Since the quartz content in the ore sample is relatively low (2.66%) and the carbonate gangue (calcite and dolomite) content is relatively high, the inhibitory effect of single sodium humate on carbonate gangue is not good, so the conventional process in this embodiment adopts a three-inhibitor combined inhibitor system, acidified water glass to inhibit quartz, and sodium humate and tannic acid to inhibit carbonate gangue. The dosage of the depressants includes 500 g / t of acidified water glass, 100 g / t of sodium humate, and 200 g / t of tannic acid. The results of the flotation tests are compared in Table 5.

[0066] In the above, the acidified water glass is prepared by mixing 250 g of sulfuric acid with 250 g of water glass (sodium silicate) and stirring uniformly.

[0067] In the above, the BHA-Ce mixture is prepared by the following method, with the steps as follows:

[0068] Benzohydroxamic acid (BHA) and cerium trichloride (CeCl3) were added into deionized water in a certain proportion, and stirred to obtain the BHA-Ce mixture; the mass ratio of the cerium trichloride to the benzohydroxamic acid was 1:30.

[0069] In the conventional flotation process of this embodiment, sodium oleate can play a foaming role.

[0070] The data in Table 4 were obtained by XRF fluorescence semi-quantitative analysis or chemical analysis method, and the analysis results were from a detection institution with detection and analysis qualification. The fluorite rough concentrate and tailing grade results in Table 4 were from the chemical analysis results of a detection institution with detection and analysis qualification, and the ore grade and the recovery rate of all products were calculated according to the recovery rate calculation formula 1:

[0071] Ore CaF2 grade = (rough concentrate CaF2 grade x rough concentrate yield + tailing CaF2 grade x tailing yield) / ore yield x 100%;

[0072] Rough concentrate CaF2 recovery rate = (rough concentrate CaF2 grade x rough concentrate yield) / (ore CaF2 grade x ore yield) x 100%;

[0073] Tailing CaF2 recovery rate = (1-rough concentrate recovery rate) x 100%.

[0074] Table 4: Main component analysis of the ore sample

[0075] Ingredients SiO2 Al2O3 CaCO3 MgO [K2O] Na2O CaF2 Content, % 2.66 7.10 50.00 3.27 1.07 2.77 32.34 Ingredients BaO Li2O Fe2O3 P2O5 Content, % 0.013 0.02 0.07 0.02

[0076] Table 5: Flotation test results

[0077]

[0078] The results show that compared with sodium oleate, the no-inhibitor process using BHA-Ce as the collector can ensure that a rough concentrate product with slightly higher grade and recovery rate is obtained, the rough concentrate yield is lower, and the enrichment ratio of fluorite is higher.

[0079] However, due to the absence of inhibitors, the flotation reagent cost will be greatly saved. Table 6 is a comparison of the reagent costs of the two flotation processes calculated at the market price. As can be seen from Table 6, the no-inhibitor process can save about 36% in reagent cost compared with the conventional process. The subsequent tailing wastewater treatment cost has not been included in the calculation.

[0080] Table 6: Comparison of flotation reagent costs of the two processes

[0081]

[0082]

[0083] In addition, the BHA-Ce collector cannot achieve good separation effect at any mass ratio of BHA and Ce, especially the proportion of cerium ions in the collector cannot be too high. Once the proportion of cerium ions is too high, it is equivalent to adding excessive cerium ions in the flotation slurry. At this time, the excessive cerium ions will be adsorbed on the gangue minerals other than fluorite due to physical adsorption, thereby losing selectivity. Eventually, other gangues and fluorite will float up at the same time, so that the mixed collector loses good selectivity to fluorite, and good separation indexes cannot be obtained.

[0084] Table 7 is the results of the non-inhibitor separation experiment of the BHA-Ce mixture collector with a mass ratio of 2:1 and a dosage of 500 g / t. The experiment is basically the same as the non-inhibitor process in Example 2, the only difference is that the mass ratio of BHA and Ce in the BHA-Ce mixture is different. From the results in Table 7, it can be seen that the selectivity of the mixture collector to fluorite under this condition is greatly reduced. Compared with the flotation results of the non-inhibitor process in Table 5, the grade and recovery of fluorite rough concentrate are greatly reduced, and even the separation effect is not as good as that of the conventional process.

[0085] Table 7 BHA: Ce = 2:1 mass ratio mixture collector non-inhibitor process flotation experiment results

[0086]

Claims

1. A beneficiation process for the flotation of fluorite without depressant, characterised in that: The method specifically comprises the following steps: Step one: the fluorite ore is ground and then added into a flotation tank, and an appropriate amount of water is added, and stirring is carried out in the flotation machine, and mixing is carried out, so as to obtain a fluorite slurry; the grinding is specifically that the fluorite ore is ground to a particle size at which the fluorite and other gangue minerals are dissociated; Step two: a certain amount of a collecting agent is added into the fluorite slurry in step one, and stirring is continuously carried out for 1-5 min; then a certain amount of a frother is added to adjust the slurry; wherein the collecting agent is a BHA-Ce mixture; Step three: air is filled, and a flotation scraping bubble operation is carried out, so as to obtain a fluorite rough concentrate and a tailing; The BHA-Ce mixture is prepared by the following method, and the steps are as follows: BHA and CeCl3 are sequentially added into deionized water according to a proportion, and stirring and mixing are carried out, so as to obtain the BHA-Ce mixture; the mass ratio of the CeCl3 to the BHA is 1:30-1:

20.

2. The method of claim 1, wherein: The amount of the collecting agent is 100-1000 g / t.

3. The method of claim 1, wherein: The mass ratio of the CeCl3 to the BHA is 1:

30.

4. The method of claim 1, wherein: The frother is any one of pinol oil or methyl isobutyl carbinol (MIBC).

5. The method of claim 1, wherein: The amount of the frother is 20-80 g / t.

6. The method of claim 1, wherein: The flotation scraping bubble time is 5-20 min.

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