Anionic and cationic combined collector and its application in flotation of andalusite

Abstract

The present invention discloses a combined anion and cation collector and its application in the flotation of andalusite. The combined anion and cation collector is made from a mixture of sodium dodecylsulfonate (an anion) and N-dodecylethylenediamine (a cation). It exhibits good water solubility and a strong selective adsorption capacity for andalusite. In particular, at a mass ratio of 1:4, the difference in recovery between andalusite, quartz, and biotite exceeds 65%, with a synergy factor greater than 1. This allows for the separation of andalusite from its associated minerals, thereby achieving enrichment of andalusite.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral flotation collectors, and particularly relates to an anion-cation combined collector and application thereof in the flotation of andalusite. Background Art

[0002] With the continuous development of my country's metallurgical and chemical industries, andalusite has become increasingly widely used and demand continues to increase. However, the relatively late development of andalusite mines in my country results in low purity, a major challenge to its industrial application. This low andalusite content is primarily due to the presence of associated minerals. During flotation, the silicate associated minerals, quartz and biotite, have similar floating properties to andalusite, making them difficult to separate and thus hindering the enrichment of andalusite.

[0003] Flotation collectors are the most important agents in mineral flotation, increasing the hydrophobicity of the mineral surface. Sodium dodecyl sulfate is an anionic collector with good water solubility and foaming properties, making it an excellent collector for andalusite. Compared to fatty acid collectors, sulfonate collectors offer greater solubility in water, resistance to low temperatures, strong resistance to hard water, strong foaming ability, and excellent flotation selectivity. Cationic collectors such as polyamines or diamines have stronger collecting abilities than dodecylamine. Dissociation produces cations with hydrophobic hydrocarbon groups, which bind to the negative charges on the mineral surface, thereby promoting flotation. Summary of the Invention

[0004] The present invention aims to provide a combined anion and cation collector that can separate andalusite from associated minerals such as quartz and biotite, thereby achieving andalusite enrichment. The combined anion and cation collector provided by the present invention can complement each other based on their unique properties, thereby generating a synergistic effect, resulting in an excellent collector with excellent capture capacity and high selectivity.

[0005] The technical solution adopted by the present invention is: an anion-cation combined collector, characterized in that the anion-cation combined collector is made of an anion collector sodium dodecylsulfonate and a cationic collector N-dodecylethylenediamine.

[0006] Preferably, the above-mentioned anion-cation combination collector has a mass ratio of N-dodecylethylenediamine:sodium dodecylsulfonate = 5:1 to 1:5.

[0007] More preferably, the above-mentioned anion-cation combination collector has a mass ratio of N-dodecylethylenediamine:sodium dodecylsulfonate = 1:4.

[0008] Preferably, the above-mentioned anion-cation combination collector, the preparation method of N-dodecylethylenediamine comprises the following steps: refluxing ethylenediamine at 55°C, slowly adding a solution of bromododecane in ethanol under reflux, and after the addition is completed, continuing to reflux at 55°C for 3 hours. After the reaction is completed, the ethylenediamine is removed by rotary evaporation, the pH of the product is adjusted to 7, filtered, washed, and dried to obtain N-dodecylethylenediamine.

[0009] Preferably, the above-mentioned anion-cation combination collector is slowly added by adding one drop every 6 to 10 seconds.

[0010] The invention provides an application of an anion-cation combined collector in the flotation of andalusite.

[0011] A method for flotation of andalusite, using the above-mentioned anion-cation combination collector, is as follows:

[0012] 1) Preparation of an anionic and cationic combined collector solution: dissolving N-dodecylethylenediamine with hydrochloric acid to obtain an N-dodecylethylenediamine hydrochloric acid solution; dissolving sodium dodecylsulfonate in water to obtain an aqueous sodium dodecylsulfonate solution; taking the N-dodecylethylenediamine hydrochloric acid solution and the aqueous sodium dodecylsulfonate solution, adjusting the pH of the mixture to 2, adding water and thoroughly mixing to obtain an anionic and cationic combined collector solution; in the anionic and cationic combined collector solution, the concentration of the anionic and cationic combined collector is 0.02 to 0.60 mg / mL, and the mass ratio of N-dodecylethylenediamine to sodium dodecylsulfonate is 5:1 to 1:5;

[0013] 2) Pre-treating the andalusite ore sample to obtain a coarse ore sample;

[0014] 3) First flotation: Mix the crude ore sample with the anion-cation combined collector solution obtained in step 1) at a solid-liquid ratio of 1 g:5-10 mL, stir at a speed of 1000-2000 r / s for 4-6 minutes, and collect the upper foam material to obtain the first flotation product;

[0015] 4) Second flotation: Add the anion-cation combined collector solution obtained in step 1) to the first flotation product again, stir at a speed of 1000-2000 r / s for 4-6 minutes, and collect the upper foam material to obtain the second flotation product;

[0016] 5) Take the second flotation product, without adding the anion and cation combined collector solution, stir at a speed of 1000-2000 r / s for 4-6 minutes, and take the upper foam material; take the obtained upper foam material, repeat this step 1-3 times, and take the final upper foam material;

[0017] 6) Magnetic separation: The upper foam material obtained in step 5) is subjected to magnetic separation using a 0.7 T strong magnetic field to obtain magnetically separated tailings and the target product andalusite.

[0018] Preferably, in the above-mentioned method for flotation of andalusite, step 2) specifically comprises: grinding the andalusite ore sample, passing it through a 200-mesh sieve, taking the sieve underfill, and then removing the ore slime with a particle size of less than 20 μm by a siphon method; and subjecting the obtained product to a single magnetic separation using a 0.7 T strong magnetic field to obtain a coarse ore sample.

[0019] Preferably, in the above-mentioned method for flotation of andalusite, in step 3) the first flotation, the crude ore sample is mixed with the anion-cation combination collector solution obtained in step 1) at a solid-liquid ratio of 1 g:5-10 mL, wherein the mass ratio of crude ore sample: anion-cation combination collector = 1 g: (1.3-1.7) mg.

[0020] Preferably, in the above-mentioned method for flotation of andalusite, in step 4), the anion-cation combination collector solution obtained in step 1) is added again to the first flotation product obtained, wherein the mass ratio of coarse ore sample: anion-cation combination collector = 1 g: (0.5-0.7) mg.

[0021] The beneficial effects of the present invention are:

[0022] 1. The anion-cation combination collector provided by the present invention, sodium dodecyl sulfate is adsorbed on the surface of andalusite through chemical action, and polyamine is adsorbed on the surface of andalusite through electrostatic action and hydrogen bonding. After the two are combined, the two adsorptions are carried out simultaneously, resulting in a synergistic effect.

[0023] 2. The combined anionic and cationic collector provided by the present invention achieves the purpose of separating and purifying andalusite by using a combination of polyamines or sodium dodecyl sulfate, compared to using either polyamine or sodium dodecyl sulfate alone. Specifically, at pH 2, with a dosage of 1.5 mg / g of the combined anionic and cationic collector and a controlled mass ratio of polyamine to sodium dodecyl sulfate of 1:4, a synergistic effect is achieved, allowing the combined collector to effectively enrich andalusite.

[0024] 3. The anion-cation combination collector provided by the present invention uses the anion-cation combination collector for andalusite mineral flotation, which provides a reference value for actual andalusite mineral flotation and has important scientific significance and practical application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic diagram of the flotation experiment using anionic and cationic combination collectors.

[0026] Figure 2 The effect of pH on the recovery of andalusite, quartz and biotite.

[0027] Figure 3 The effect of the dosage of anion and cation combined collector on the recovery rate of andalusite, quartz and biotite.

[0028] Figure 4 The effect of different mass ratios of anion and cation combined collectors on the recovery rates of andalusite, quartz and biotite.

[0029] Figure 5 It is the synergistic effect on andalusite flotation under different mass ratios.

[0030] Figure 6 This is the flotation flow chart in Example 2.

[0031] Figure 7 These are images of the andalusite sample in Example 2 magnified 25 times and 100 times under a polarizing microscope. DETAILED DESCRIPTION

[0032] The present invention will be further described below with reference to specific examples, but is not limited thereto.

[0033] Example 1 A method for flotation of andalusite

[0034] In this embodiment, single mineral experiments were conducted on pure andalusite, pure quartz, and pure biotite, respectively, to screen the conditions.

[0035] (1) Effect of pH on mineral flotation behavior

[0036] 1. Preparation of N-dodecylethylenediamine

[0037] Place 50 mL of ethylenediamine in a three-necked flask and reflux at 55°C. Weigh 2.4923 g of dodecane bromide and completely dissolve it in 30 mL of ethanol. Place the solution in a constant-pressure dropping funnel, insert the funnel into the three-necked flask, and slowly add the dodecane bromide ethanol solution dropwise at a rate of one drop every 6-10 seconds under reflux. After the dodecane bromide solution is added, continue the reaction at 55°C for 3 hours. After the reaction is complete, remove the solvent and ethylenediamine by rotary evaporation. Adjust the pH to 7 with hydrochloric acid. A white solid will precipitate. Wash with deionized water, centrifuge, and dry to obtain N-dodecylethylenediamine, designated as a polyamine.

[0038] 2. Flotation method

[0039] 2.1) Preparation of anion and cation combination collector solution: Dissolve polyamine in 1M hydrochloric acid solution to obtain a polyamine hydrochloric acid solution with a concentration of 2 mg / mL. Dissolve sodium dodecyl sulfate in water to obtain an aqueous sodium dodecyl sulfate solution with a concentration of 1 mg / mL. Take 3.33 mL of polyamine hydrochloric acid solution and 3.33 mL of sodium dodecyl sulfate aqueous solution, adjust the pH of the mixed solution to 2, 3, 4, 5, 6, 7, 8, and 9 with hydrochloric acid or NaOH, and then dilute to 100 mL with water to obtain anion and cation combination collector solutions of different pH values. In the anion and cation combination collector solution, the concentration of the anion and cation combination collector is 0.10 mg / mL, and the mass ratio of polyamine: sodium dodecyl sulfate is 2:1.

[0040] 2.2) Take 20mL of anion and cation combination collector solutions of different pH values ​​at a concentration of 0.10mg / mL and pour them into a 20mL XFGC flotation tank containing 2g of pure andalusite monomineral. Set the speed to 1992r / s, do not inflate, and flotation for 4min. During the flotation process, use a flotation brush to continuously brush out the upper foam material. After flotation, the upper foam material floated out is washed with deionized water, dried, and weighed to calculate the recovery rate of andalusite.

[0041] 2.3) Comparative Example 1 - 20 mL of a 0.10 mg / mL solution of a combined anion and cation collector at different pH values ​​was poured into a 20 mL XFGC flotation cell containing 2 g of pure quartz. The flotation was performed at a speed of 1992 rpm, without aeration, for 4 minutes. During flotation, a flotation brush was used to continuously remove the upper foam. After flotation, the upper foam was washed with deionized water, dried, and weighed to calculate the quartz recovery rate.

[0042] 2.4) Comparative Example 2 - 20 mL of a 0.10 mg / mL solution of a combined anion and cation collector with varying pH values ​​was poured into a 20 mL XFGC flotation cell containing 2 g of pure biotite. The flotation speed was set at 1992 rpm, without aeration, and the flotation process was continued for 4 minutes. During the flotation process, the upper foam was continuously removed with a flotation brush. After the flotation, the upper foam was washed with deionized water, dried, and weighed to calculate the biotite recovery rate.

[0043] Flotation experiment operation Figure 1 , the results are as follows Figure 2 .

[0044] like Figure 1 As shown, during flotation, adjust the rotation speed. When the foam covers the interface, use the flotation brush to scrape the foam from left to right into the beaker.

[0045] from Figure 2As can be seen, at pH 6, the andalusite recovery rate reaches a maximum of 47.57%. However, the quartz recovery rate is even higher at this point, at 68%, making it impossible to separate andalusite from quartz. At pH 2, the andalusite recovery rate is 34%, and the other two minerals are barely flotated. Although the flotation recovery rate of andalusite with the anionic and cationic combination collector is not high at pH 2, the selectivity is good. Therefore, the present invention prefers a pH of 2 for the anionic and cationic combination collector solution.

[0046] (2) Effect of the dosage of anionic and cationic combined collectors on mineral flotation behavior

[0047] 1. Preparation of N-dodecylethylenediamine: Same as (1)

[0048] 2. Flotation method:

[0049] 2.1) Preparation of anion and cation combination collector solution: Dissolve polyamine in 1M hydrochloric acid solution to obtain a polyamine hydrochloric acid solution with a concentration of 2 mg / mL. Dissolve sodium dodecyl sulfate in water to obtain a sodium dodecyl sulfate aqueous solution with a concentration of 1 mg / mL. Take appropriate amounts of polyamine hydrochloric acid solution and appropriate amounts of sodium dodecyl sulfate aqueous solution, adjust the pH of the mixed solution to 2 with hydrochloric acid or NaOH, and then dilute to 100 mL with water to obtain anion and cation combination collector solutions of different concentrations. In the anion and cation combination collector solution, the concentrations of the anion and cation combination collectors are 0.020, 0.05, 0.07, 0.10, 0.12, 0.15, 0.18, 0.20, 0.40, and 0.60 mg / mL, respectively, and by mass ratio, polyamine: sodium dodecyl sulfate = 2:1.

[0050] 2.2) Take 20mL of a solution of an anion and cation combination collector with a pH of 2 and a concentration of 0.020, 0.05, 0.07, 0.1, 0.12, 0.15, 0.18, 0.20, 0.40, and 0.60mg / mL, and pour it into a 20mL XFGC flotation tank containing 2g of pure andalusite. Set the speed to 1992r / s, do not inflate, and float for 4min. During the flotation process, use a flotation brush to continuously brush out the upper foam material. After flotation, the upper foam material floated out is washed with deionized water, dried, and weighed to calculate the recovery rate of andalusite. (Equivalent to adding 0.2, 0.5, 0.7, 1.0, 1.2, 1.5, 1.8, 2.0, 4.0, and 6.0mg of anion and cation combination collector per gram of pure andalusite).

[0051] 2.3) Comparative Example 3: 20 mL of a pH 2 solution of a combined anion and cation collector solution containing concentrations of 0.020, 0.05, 0.07, 0.10, 0.12, 0.15, 0.18, 0.20, 0.40, and 0.60 mg / mL was poured into a 20 mL XFGC flotation cell containing 2 g of pure quartz. The speed was set to 1992 r / s, without aeration, and flotation was performed for 4 minutes. During the flotation process, a flotation brush was used to continuously remove the upper foam material. After flotation, the upper foam material was washed with deionized water, dried, and weighed to calculate the recovery rate of quartz. (This is equivalent to adding 0.2, 0.5, 0.7, 1.0, 1.2, 1.5, 1.8, 2.0, 4.0, and 6.0 mg of the combined anion and cation collector per gram of pure quartz, respectively).

[0052] 2.4) Comparative Example 4 - 20 mL of a pH 2 solution of a combined anion and cation collector at concentrations of 0.020, 0.05, 0.07, 0.10, 0.12, 0.15, 0.18, 0.20, 0.40, and 0.60 mg / mL was poured into a 20 mL XFGC flotation cell containing 2 g of pure biotite. The flotation speed was set to 1992 r / s, without aeration, and flotation was performed for 4 minutes. During flotation, the upper foam material was continuously removed with a flotation brush. After flotation, the upper foam material was washed with deionized water, dried, and weighed to calculate the biotite recovery rate. (This corresponds to adding 0.2, 0.5, 0.7, 1.0, 1.2, 1.5, 1.8, 2.0, 4.0, and 6.0 mg of the combined anion and cation collector per gram of pure biotite, respectively.)

[0053] Flotation experiment operation Figure 1 , the results are as follows Figure 3 .

[0054] from Figure 3 It can be seen that the recovery rates of both andalusite and biotite by the combined anion and cation collector initially increase and then remain stable with increasing collector dosage. At a collector dosage of 4 mg / g, the recovery rate of andalusite reaches over 95%, while a higher dosage is required for biotite. The combined collector's recovery rate for quartz is less than 5%, indicating its extremely poor quartz mineral capture ability. Theoretically, it can effectively separate andalusite from quartz. At a collector dosage of 1.5 mg / g, the recovery rate of andalusite reaches over 55%, while biotite and quartz have recoveries of less than 5%, resulting in a single-mineral flotation difference of approximately 50%. Therefore, the preferred dosage of the combined anion and cation collector in the present invention is 1.3 to 1.7 mg of combined anion and cation collector per gram of andalusite sample.

[0055] (III) Effect of the mass ratio of anion and cation combined collectors on mineral flotation behavior

[0056] 1. Preparation of N-dodecylethylenediamine: Same as (1)

[0057] 2. Flotation method:

[0058] 2.1) Preparation of anion and cation combination collector solution: Dissolve polyamine with 1M hydrochloric acid solution to obtain a polyamine hydrochloric acid solution with a concentration of 2 mg / mL. Dissolve sodium dodecyl sulfate in water to obtain a sodium dodecyl sulfate aqueous solution with a concentration of 1 mg / mL. Take appropriate amounts of polyamine hydrochloric acid solution and appropriate amount of sodium dodecyl sulfate aqueous solution, adjust the pH of the mixed solution to 2 with hydrochloric acid or NaOH, and then dilute to 100 mL with water to obtain anion and cation combination collector solutions with different mass ratios of polyamine to sodium dodecyl sulfate. In the anion and cation combination collector solution, the concentration of the anion and cation combination collector is 0.10 mg / mL, and by mass ratio, polyamine: sodium dodecyl sulfate = 5:0, 4:1, 2:1, 1:1, 1:2, 1:4, 5:0.

[0059] 2.2) Take 20mL of anion and cation combination collector solution with a pH of 2 and a concentration of 0.10mg / mL of different polyamine and sodium dodecyl sulfate mass ratios, pour it into a 20mL XFGC flotation tank containing 2g of pure andalusite monomineral, set the speed to 1992r / s, do not inflate, and float for 4min. During the flotation process, a flotation brush is used to continuously brush out the upper foam material. After flotation, the upper foam material floated out is washed with deionized water, dried, and weighed to calculate the recovery rate of andalusite.

[0060] 2.3) Comparative Example 5 - 20 mL of a 0.10 mg / mL solution of anionic and cationic collectors with different polyamine to sodium dodecyl sulfate mass ratios at pH 2 was poured into a 20 mL XFGC flotation cell containing 2 g of pure quartz. The flotation was performed at a speed of 1992 rpm, without aeration, for 4 minutes. During flotation, the upper foam was continuously removed with a flotation brush. After flotation, the upper foam was washed with deionized water, dried, and weighed to calculate the quartz recovery rate.

[0061] 2.4) Comparative Example 6 - 20 mL of a 0.10 mg / mL solution of anionic and cationic collectors with different polyamine to sodium dodecyl sulfate mass ratios at pH 2 was poured into a 20 mL XFGC flotation cell containing 2 g of pure biotite. The flotation was performed at a speed of 1992 rpm, without aeration, for 4 minutes. During flotation, the upper foam was continuously removed with a flotation brush. After flotation, the upper foam was washed with deionized water, dried, and weighed to calculate the biotite recovery rate.

[0062] Flotation experiment operation Figure 1 , the results are as follows Figure 4 The synergistic factors of andalusite, quartz and biotite in different mass ratios of combined collectors were calculated. The results are as follows: Figure 5 .

[0063] from Figure 4 It can be seen that under these conditions, when polyamines or sodium dodecyl sulfate are used alone as collectors, the recoveries of andalusite and biotite are significantly higher than those of quartz. While theoretically effective separation of quartz is possible, the biotite recovery remains high. Experimenting with different mass ratios effectively increases the difference between the recoveries of andalusite and biotite. When the mass ratio of polyamine to sodium dodecyl sulfate is 4:1, the recovery of biotite is higher than that of andalusite. At mass ratios of 2:1, 1:1, 1:2, and 1:4, the recovery of andalusite is higher than that of biotite. At a mass ratio of 1:1, the recovery rates of both are low and similar. The difference in recovery rates between the two is significant at mass ratios of 2:1, 1:2, and 1:4, particularly at a mass ratio of 1:4, where the difference reaches over 65%, enabling separation of andalusite from biotite and thus enrichment of andalusite.

[0064] from Figure 5 It can be seen that when the mass ratio of polyamine to sodium dodecyl sulfate is 1:4, the synergy factor is greater than 1, indicating a synergistic effect of the combined collector on andalusite flotation. At other mass ratios, the synergy factor is less than 1, indicating an anti-synergistic effect. Example 2: A Method for Flotation of Andalusite (I) The andalusite mineral used in this example was powdered ore provided by an andalusite manufacturer in Liaoning. The XRF analysis results of the actual mineral are shown in Table 1.

[0065] Table 1 XRF analysis results of actual minerals (%)

[0066]

[0067] As shown in Table 1, XRF semi-quantitative analysis indicates that the andalusite ore contains a high content of Al2O3, reaching 51.04%, and a high content of Fe2O3. Therefore, it requires mineral processing and purification before it can be used.

[0068] The andalusite used is carbonaceous andalusite two-mica schist. Figure 7 , a clear structure can be seen through a polarizing microscope. Figure 7 The rock is gray-black with a porphyritic structure. The phenocrysts are composed of andalusite, which are semi-euhedral long columns or euhedral quadrilaterals. The matrix has a scaly granular metamorphic structure and a lamellae-like texture. The hand-stained specimen contains carbonaceous components.

[0069] Matrix ingredients:

[0070] Muscovite: colorless, flaky aggregate, replacing andalusite. Accounts for about 10%.

[0071] Biotite: Long, yellowish-brown flakes, oriented around andalusite to form foliation. It accounts for about 25%.

[0072] Quartz: Heteromorphic granular, coexisting with biotite. Particle size: 0.05-0.5mm, accounting for about 15%.

[0073] Carbonaceous components: black, particle-like, cryptocrystalline aggregates, accounting for about 15-20%.

[0074] (2) The method for flotation of andalusite is as follows:

[0075] 1) Preparation of anion and cation combined collector solution:

[0076] Dissolve polyamine in 1M hydrochloric acid solution to obtain a polyamine hydrochloric acid solution with a concentration of 2 mg / mL. Dissolve sodium dodecyl sulfate in water to obtain a sodium dodecyl sulfate aqueous solution with a concentration of 1 mg / mL. Take 30 mL of polyamine hydrochloric acid solution and 240 mL of sodium dodecyl sulfate aqueous solution, adjust the pH of the mixed solution to 2 with hydrochloric acid or NaOH, and then dilute to 1000 mL with water to obtain an anion-cation combination collector solution. In the anion-cation combination collector solution, the concentration of the anion-cation combination collector is 0.30 mg / mL, and the mass ratio of polyamine to sodium dodecyl sulfate is 1:4.

[0077] 2) Pre-treating the andalusite ore sample to obtain a coarse ore sample; specifically:

[0078] 2.1) Classification: Grind the andalusite sample, pass it through a 200-mesh sieve, and take the sieve residue.

[0079] 2.2) Desludging: Quarter sampling, measure 10 mL of ore sample with a measuring cup, weigh it, and calculate the density of the ore sample to be 1.16621 g / cm 3 The ore sample obtained in the previous step was desludified using the siphon method and calculated according to the formula:

[0080]

[0081] Calculate the desludging time to remove particles with a size of approximately 20 μm or less. In the formula, d is the graded particle size, h is the material settling height, ρ1 is the density of the ore sample, ρ is the density of water, g is the acceleration due to gravity, μ is the viscosity of water, and t is the time required.

[0082] 2.3) Magnetic attraction method to remove magnetic materials: The desludging product is subjected to a magnetic separation using a 0.7T strong magnetic field to obtain a coarse ore sample.

[0083] 3) First Flotation: 330 mL of the anionic and cationic collector solution prepared in step 1) (pH 2, concentration 0.30 mg / mL, and a polyamine to sodium dodecyl sulfate mass ratio of 1:4) was poured into a 500 mL XFGC flotation cell containing 66 g of the crude ore sample. The flotation process was performed at a speed of 1992 rpm, without aeration, for 4 minutes. During the flotation process, the upper foamy material was continuously removed with a flotation brush to obtain the first flotation product.

[0084] 4) Second flotation: To the first flotation product, 132 mL of the anionic and cationic combined collector solution prepared in step 1) having a pH of 2, a concentration of 0.30 mg / mL, and a mass ratio of polyamine to sodium dodecyl sulfate of 1:4 was added. The mixture was stirred at a speed of 1992 r / s for 4 min, and the upper foam material was collected to obtain the second flotation product.

[0085] 5) Take the second flotation product, without adding the anionic and cationic combined collector solution, and stir at 1992 rpm for 4 minutes. Then take the upper foam material. Repeat this step twice, taking the final upper foam material.

[0086] 6) Magnetic separation: The upper foam material obtained in step 5) is subjected to magnetic separation using a 0.7 T strong magnetic field to obtain magnetically separated tailings and the target product andalusite.

[0087] The target product andalusite has an Al2O3 grade of 56.22%, an Al2O3 recovery rate of 17.96%, and a Fe2O3 content of 0.86%, meeting the HZ-56 standard in the current national industry YB / T 4032-2010.

Claims

1. A combined anion and cation collector for flotation of andalusite, characterized in that: The anionic and cationic combined collector for flotation of andalusite is prepared from anionic collector sodium dodecylsulfonate and cationic collector N-dodecylethylenediamine; the mass ratio of N-dodecylethylenediamine to sodium dodecylsulfonate is 1:

4.

2. The anion-cation combined collector for flotation of andalusite according to claim 1, characterized in that: The preparation method of N-dodecylethylenediamine comprises the following steps: refluxing ethylenediamine at 55°C, slowly adding a solution of bromododecane in ethanol dropwise under reflux, continuing to reflux at 55°C for 3 hours after the addition is complete, removing ethylenediamine by rotary evaporation after the reaction is complete, adjusting the pH of the product to 7, filtering, washing, and drying to obtain N-dodecylethylenediamine.

3. The anion-cation combined collector for flotation of andalusite according to claim 2, characterized in that: The slow dropwise addition is to add one drop every 6 to 10 seconds.

4. Use of the anion-cation combined collector for flotation of andalusite according to any one of claims 1 to 3 in flotation of andalusite.

5. A method for flotation of andalusite, characterized in that: The method of using the anion-cation combined collector for flotation of andalusite according to any one of claims 1 to 3 is as follows: 1) Preparation of an anionic and cationic combined collector solution: N-dodecylethylenediamine is dissolved in hydrochloric acid to obtain an N-dodecylethylenediamine hydrochloric acid solution; sodium dodecylsulfonate is dissolved in water to obtain an aqueous sodium dodecylsulfonate solution; the pH of the N-dodecylethylenediamine hydrochloric acid solution and the aqueous sodium dodecylsulfonate solution are adjusted to 2, and water is added and mixed thoroughly to obtain an anionic and cationic combined collector solution; the concentration of the anionic and cationic combined collector solution is 0.02 to 0.60 mg / mL, and the mass ratio of N-dodecylethylenediamine to sodium dodecylsulfonate is 1:4; 2) Pre-treating the andalusite ore sample to obtain a crude ore sample; 3) First flotation: Mix the crude ore sample with the anion-cation combined collector solution obtained in step 1) at a solid-liquid ratio of 1 g: 5-10 mL. Stir at a speed of 1000-2000 r / s for 4-6 minutes. Collect the upper foam material to obtain the first flotation product. 4) Second flotation: Add the anion-cation combined collector solution obtained in step 1) to the first flotation product again, stir at a speed of 1000-2000 r / s for 4-6 minutes, and collect the upper foam material to obtain the second flotation product; 5) Take the second flotation product, without adding the anion and cation combined collector solution, stir at a speed of 1000-2000 r / s for 4-6 minutes, and collect the upper foam material; take the obtained upper foam material, repeat this step 1-3 times, and collect the final upper foam material; 6) Magnetic separation: The upper foam material collected in step 5) is subjected to magnetic separation using a strong magnetic field of 0.7 T to obtain magnetically separated tailings and the target product, andalusite.

6. The method for flotation of andalusite according to claim 5, characterized in that: Step 2) specifically comprises: grinding the andalusite ore sample, passing it through a 200-mesh sieve, taking the sieve underfill, and then removing the ore slime with a particle size of less than 20 μm by a siphon method; the resulting product is subjected to a single magnetic separation using a 0.7 T strong magnetic field to obtain a coarse ore sample.

7. The method for flotation of andalusite according to claim 5, characterized in that: Step 3) In the first flotation, the crude ore sample is mixed with the anion-cation combination collector solution obtained in step 1) at a solid-liquid ratio of 1 g: 5-10 mL, wherein the mass ratio of crude ore sample: anion-cation combination collector is 1 g: (1.3-1.7) mg.

8. The method for flotation of andalusite according to claim 5, characterized in that: In step 4), the anion-cation combination collector solution obtained in step 1) is added again to the first flotation product, wherein the mass ratio of coarse ore sample: anion-cation combination collector = 1 g: (0.5-0.7) mg.

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