Selective fluorite flotation collector and preparation method thereof

Abstract

The invention relates to the technical field of mineral flotation agents, in particular to a selective fluorite flotation collector and a preparation method thereof, and the selective fluorite flotation collector is formed by electrostatic bonding of an organic matter containing protonated amino and an organic matter containing deprotonated groups; under the neutral and acidic conditions, the collecting agent is successfully assembled to form a pseudo-gemini structure, the surface hydrophobicity of minerals is enhanced, efficient collection of fluorite at low concentration can be achieved, the yield of concentrate is increased, and the purpose of roughing is achieved; under the alkaline condition, the collecting agent is decoupled into the anion form of a monomolecular organic matter containing amido and the anion form of a monomolecular organic matter containing deprotonated groups, the organic matter containing amido continues to play a role in collecting fluorite, the anion form of the organic matter containing deprotonated groups reacts with calcite, surface active sites of calcite are reduced, and the fluorite collecting effect is improved. Calcite flotation is inhibited, the mineral selectivity is improved, the fluorite flotation recovery rate is increased, the separation efficiency is improved, and the purpose of concentration is achieved.

Description

Technical Field

[0001] This invention relates to the field of mineral flotation agent technology, and in particular to a selective fluorite flotation collector and its preparation method. Background Technology

[0002] Flotation is currently the main method for separating fluorite from gangue minerals, and its efficiency is highly dependent on the compatibility of the collector system. However, existing flotation technologies have limitations in practical applications, mainly including: the chemical properties of the interface between fluorite and calcite minerals are similar, and their surface active sites are both Ca. 2+ The main problem is competitive adsorption in traditional fatty acid collector systems, leading to separation difficulties; and the F produced during mineral dissolution during flotation... - (fluorite) and CO3 2- Calcite will compete with collectors for coordination, reducing the effective concentration of the agent.

[0003] Furthermore, existing collectors have significant drawbacks in practical applications: anionic collectors (such as oleic acid and sodium hexadecyl sulfate) are chemically active and have good flotation effects, but they have poor selectivity, are not resistant to hard water, and are not easy to disperse; cationic collectors (such as dodecylamine and etheramine) require complex processes, and their flotation effects are easily affected by the pulp concentration; amphoteric collectors (such as dodecylaminoacetic acid) have a wide applicable pH range, but their synthesis is difficult and their cost is high, which limits their widespread application.

[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a selective fluorite flotation collector and its preparation method, aiming to solve the problems of poor selectivity and low separation efficiency of existing fluorite flotation collectors.

[0006] The technical solution of the present invention is as follows:

[0007] A selective fluorite flotation collector is formed by electrostatic bonding of an organic compound containing a protonated amine group and an organic compound containing a deprotonated group;

[0008] The general structural formula of the organic compound containing the protonated amine group is R. + —(CH2) m CH3, R + It is a protonated amino group, (CH2) m CH3 is a hydrophobic chain, m = 12-18, and m is an integer;

[0009] The general structural formula of the organic compound containing the deprotonated group is [Core]-(X - ) nCore is the central framework, X - For a deprotonating group, n≥2, and n is an integer.

[0010] The selective fluorite flotation collector, wherein the protonated amine group includes -NH3. + -NH2 + -、-N + One or more of (CH3)3.

[0011] The selective fluorite flotation collector, wherein the deprotonating group includes -COO - -SO3 - One or more of them.

[0012] The selective fluorite flotation collector, wherein the central framework comprises at least one of C2-C10 alkyl groups, benzene rings, and cyclohexane.

[0013] The selective fluorite flotation collector wherein the protonated amine-containing organic compound is selected from at least one of protonated dodecaneamine hydrochloride, protonated hexadecaneamine hydrochloride, and protonated hexadecyltrimethylammonium bromide.

[0014] The selective fluorite flotation collector wherein the organic compound containing the deprotonating group is selected from at least one of deprotonated citric acid, deprotonated oxalic acid, deprotonated ethylenediaminetetraacetic acid, and deprotonated 1,5-naphthalenedisulfonic acid.

[0015] The selective fluorite flotation collector wherein the molar ratio of the organic compound containing protonated amine groups to the organic compound containing deprotonated groups is (1-4):1.

[0016] A method for preparing a selective fluorite flotation collector, comprising the following steps:

[0017] Organic compounds containing amine groups and organic compounds containing deprotonable groups are mixed with water to obtain a mixed solution;

[0018] The mixed solution was subjected to ultrasonic treatment, followed by heating and stirring to adjust the pH value, thereby obtaining a selective fluorite flotation collector.

[0019] The method for preparing the selective fluorite flotation collector, wherein the molar ratio of the amine-containing organic compound to the organic compound containing the deprotonable group is (1-4):1.

[0020] The method for preparing the selective fluorite flotation collector includes a heating and stirring treatment at a temperature of 50°C-60°C for 30-60 minutes and a pH value between 5 and 7.

[0021] Beneficial effects: This invention provides a selective fluorite flotation collector and its preparation method. The selective fluorite flotation collector is formed by electrostatic bonding of an organic compound containing a protonated amine group and an organic compound containing a deprotonated group; wherein the general structural formula of the organic compound containing the protonated amine group is R. + —(CH2) m CH3, R + It is a protonated amino group, (CH2) m CH3 is a hydrophobic chain, m = 12-18; the general structural formula of the organic compound containing the deprotonated group is [Core]-(X - ) n Core is the central framework, X - The term "n" refers to a deprotonated group, where n ≥ 2. This invention utilizes organic compounds containing protonated amine groups and organic compounds containing deprotonated groups to synthesize a selective fluorite flotation collector through electrostatic pairing. Under neutral and acidic conditions, the collector successfully assembles, forming a pseudo-gemini structure, enhancing the hydrophobicity of the mineral surface. This enables efficient collection of fluorite at low concentrations, increasing concentrate yield and achieving the purpose of roughing. Under alkaline conditions, the collector decouples into anionic forms of single-molecule organic compounds containing amine groups and organic compounds containing deprotonated groups. The amine-containing organic compounds continue to collect fluorite, while the anionic form of the deprotonated organic compounds reacts with calcite, reducing active sites on the calcite surface, inhibiting calcite flotation, improving mineral selectivity, enhancing fluorite flotation recovery, increasing separation efficiency, and achieving the purpose of fine cleaning. Attached Figure Description

[0022] Figure 1 This is a diagram showing the ionization distribution of citric acid.

[0023] Figure 2 This is a process flow diagram of a selective fluorite flotation collector preparation method according to the present invention;

[0024] Figure 3 DH-CA xy Structural diagram;

[0025] Figure 4 Here is a flowchart of the flotation process;

[0026] Figure 5 DH-CA collector 21 Graph showing the effect of DH concentration on the recovery rates of CaF2 and CaCO3 in single mineral flotation. Detailed Implementation

[0027] This invention provides a selective fluorite flotation collector and its preparation method. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0028] It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should also be understood that terms such as those defined in general dictionaries should be understood to have the same meaning as in the context of the prior art, and should not be interpreted in an idealized or overly formal sense unless specifically defined as herein.

[0029] In the existing technical field, various flotation separation methods for fluorite have been developed. For example, patent CN116943871B discloses a highly efficient collector for the flotation of high-calcium fluorite. This collector uses benzohydroxyxamic acid and cerium trichloride as raw materials to synthesize BHA-Ce metal complexes and BHA-Ce mixtures, which can effectively improve the selectivity of fluorite. However, this composite collector has a complex composition, a long reaction time, and reagent loss during the synthesis process, resulting in a low composite yield. Another example is patent CN119368336A, which achieves efficient fluorite recovery through the synergistic effect of collectors, modifiers, and inhibitors. The collector is composed of alkyl phosphate, alkylamino carboxylic (sulfonic) acid, and α-nitroso-β-naphthol, while the inhibitors include water glass, lignin sulfonic acid, and picric acid. This method can achieve high-grade and high-recovery rates of fluorite, but the process is complex, requires a large amount of reagents, and has shortcomings in terms of environmental protection and economic efficiency. In addition, the molecular structures and mechanisms of action of the flotation reagents mentioned above are relatively traditional and fixed, their pH range is narrow, and they lack special designs for the separation of fluorite and calcite.

[0030] Based on this, the present invention proposes a selective fluorite flotation collector, which is formed by electrostatic bonding of an organic compound containing a protonated amine group and an organic compound containing a deprotonated group.

[0031] The general structural formula of the organic compound containing the protonated amine group is R. + —(CH2) m CH3, R + It is a protonated amino group, (CH2) m CH3 is a hydrophobic chain, m = 12-18, and m is an integer;

[0032] The general structural formula of the organic compound containing the deprotonated group is [Core]-(X - ) n Core is the central framework, X- For a deprotonating group, n≥2, and n is an integer.

[0033] In this embodiment, a selective fluorite flotation collector is synthesized by electrostatic pairing of an organic compound containing a protonated amine group and an organic compound containing a deprotonated group. Under neutral and acidic conditions, the collector successfully assembles to form a pseudo-gemini structure, enhancing the hydrophobicity of the mineral surface and enabling efficient collection of fluorite at low concentrations, thereby increasing concentrate yield and achieving the purpose of roughing. Under alkaline conditions, the collector decouples into anionic forms of a single-molecule organic compound containing an amine group and an organic compound containing a deprotonated group. The organic compound containing the amine group continues to collect fluorite, while the anionic form of the organic compound containing the deprotonated group reacts with calcite, reducing the active sites on the calcite surface, inhibiting calcite flotation, improving mineral selectivity, enhancing fluorite flotation recovery, improving separation efficiency, and achieving the purpose of fine cleaning.

[0034] Specifically, the selective fluorite flotation collector of the present invention is formed by electrostatic attraction or hydrogen bonding between polar groups (i.e., deprotonated groups) of spacer molecules with opposite charges and hydrophobic tail molecules (i.e., protonated amine groups). By changing the number of carbon chains in the polar groups and hydrophobic tail molecules of the spacer, pseudo-gemini collectors with different molecular formulas can be obtained. The pseudo-gemini structure is formed by ion pairing of organic matter containing protonated amine groups and organic matter containing deprotonated groups. This structure has pH-responsive characteristics and has multiple hydrophobic alkyl chains under neutral and acidic conditions, which can significantly enhance the hydrophobicity of the mineral surface, thereby achieving efficient flotation at low concentrations and greatly reducing the amount of collector used. In other words, by adjusting the pH value of the selective fluorite flotation collector, a flotation process is achieved that improves concentrate yield in roughing under neutral and acidic conditions and enhances concentrate recovery in cleaning under alkaline conditions. The overall technical effect is significant, not only reducing the amount of collector used but also achieving efficient separation of fluorite and calcite, while reducing the amount of traditional inhibitor sodium hexametaphosphate used, thus offering advantages in efficiency, environmental friendliness, and economy. Furthermore, compared to traditional collectors, this type of collector has an extremely low critical micelle concentration (CMC), high solubilization capacity, and good wetting and foaming properties, which can significantly reduce the surface tension of water and the oil-water interfacial tension, thereby achieving efficient separation of fluorite and calcite.

[0035] In some embodiments, the protonated amine group includes -NH3. + -NH2 + -、-N +One or more of (CH3)3. Under acidic or neutral conditions, it can cause organic compounds containing protonated amine groups to undergo ion pairing with organic compounds containing deprotonated groups to form pseudo-gemini structures, thereby enhancing the hydrophobicity of mineral surfaces, increasing concentrate yield, and achieving the purpose of roughing. Under alkaline conditions, the selective fluorite flotation collector can decouple into organic compounds with amine groups to continue collecting fluorite.

[0036] In some embodiments, the deprotonating group includes -COO - -SO3 - One or more of the following. It can act as a "spacer" to link multiple long cationic chains. Under acidic or neutral conditions, it can electrostatically combine organic compounds containing protonated amine groups with organic compounds containing deprotonated groups to form a selective fluorite flotation collector. Under alkaline conditions, it can decouple into the anionic form of organic compounds containing deprotonated groups, which forms a stable complex with calcium ions on the calcite surface, reducing the active sites on the calcite surface, inhibiting calcite flotation, improving mineral selectivity, increasing fluorite flotation recovery, and achieving the purpose of fine selection.

[0037] In some embodiments, the central skeleton includes at least one of C2-C10 alkyl groups, benzene rings, and cyclohexane.

[0038] In some embodiments, the protonated amine-containing organic compound is selected from protonated dodecaneamine hydrochloride (DH) and protonated hexadecaneamine hydrochloride (C). 16 H 33 NH3 + Cl - At least one of the following: protonated hexadecyltrimethylammonium bromide (CTAB).

[0039] In some embodiments, the organic compound containing the deprotonated group is selected from at least one of deprotonated citric acid (CA), deprotonated oxalic acid (HOOC-COOH), deprotonated ethylenediaminetetraacetic acid (EDTA, containing 4 carboxyl groups), and deprotonated 1,5-naphthalenedisulfonic acid (containing two -SO3H groups).

[0040] In a preferred embodiment, the protonated amine-containing organic compound is protonated dodecaneamine hydrochloride (DH), and the deprotonated organic compound is deprotonated citric acid (CA). DH and CA pair via electrostatic interaction to synthesize DH-CA. xy Where x represents the molar number of dodecylammonium ions and y represents the molar number of citrate anions. DH-CA xyA pseudo-gemini structure is formed by pairing protonated dodecaneamine hydrochloride (DH) with deprotonated citrate (CA) ions. This structure exhibits pH-responsive characteristics and possesses multiple hydrophobic alkyl chains under neutral and acidic conditions, significantly enhancing the hydrophobicity of mineral surfaces. This enables highly efficient flotation at low concentrations, drastically reducing collector dosage. Under alkaline conditions, DH-CA... xy The decoupling process results in single molecules of dodecaneamine and citrate anions. Dodecaneamine continues to act as a collector, while citrate anions react with calcite, reducing the active sites on the calcite surface and thus enhancing the flotation selectivity of fluorite and calcite.

[0041] Specifically, under neutral and acidic conditions, dodecylamine hydrochloride is protonated to form a positively charged dodecylammonium ion, and citric acid is deprotonated to form a negatively charged citrate anion, DH-CA xy Successful assembly forms a pseudo-gemini structure, enhancing the hydrophobicity of the mineral surface, increasing concentrate yield, and achieving the purpose of roughing. Under alkaline conditions, deprotonated dodecaneamine hydrochloride and similarly deprotonated citric acid no longer undergo ion pairing, DH-CA... xy The decoupling occurs as dodecaneamine and citrate anions. Dodecaneamine continues to capture fluorite, while the citrate anions react with Ca on the calcite surface. 2+ It forms stable complexes, reduces the active sites on the calcite surface, inhibits calcite flotation, improves mineral selectivity, increases fluorite flotation recovery, and achieves the purpose of fine selection.

[0042] For example, in fluorite flotation, dodecaneamine hydrochloride, as a cationic collector, can enhance the hydrophilicity-hydrophobicity difference between the surfaces of fluorite and calcite. Citric acid (C6H8O7) is a tricarboxylic acid containing three carboxyl groups (-COOH) and one hydroxyl group (-OH). By changing the pH of the solution, these groups undergo proton exchange (H+). + The release or combination of these molecules forms ions with different valences, whose pKa values ​​are approximately 2.6, 4.3, and 6.5, respectively. Figure 1 This is a diagram showing the ionization distribution of citric acid. At low pH, citric acid exists in a fully protonated form (C6H8O7). As pH increases, the carboxyl group gradually deprotonates, forming a single-charged ion (C6H7O7). - ), double-charged ions (C6H6O7) 2- Under strongly alkaline conditions, all carboxyl groups are deprotonated, forming tricharged ions (C6H5O7). 3- Dodecylamine hydrochloride contains only one protonable amino site with a pKa of 10.6. At pH less than 10.6, a protonated dodecylammonium ion (C1) is present. 12 H 25 NH3 +As pH increases, dodecylammonium ions gradually deprotonate to form dodecylamine (C12- ... 12 H 25 (NH2). When the pH is above 10.6, dodecylammonium ions are completely deprotonated and exist as dodecylamine. Therefore, by adjusting the pH of the reagents and the flotation pulp, protonated DH and deprotonated CA can be assembled into pseudo-gemini collectors DH-CA in different molar ratios at different pH ranges. xy .

[0043] In some embodiments, the molar ratio of the protonated amine-containing organic compound to the deprotonated organic compound is (1-4):1. Based on the dissociation behavior at different pH values, selective fluorite flotation collectors with different molar ratios can be assembled by electrostatic attraction.

[0044] Take DH-CA xy For example, when pH = 3-5, it assembles into DH-CA. 11 When pH = 5-7, it assembles into DH-CA. 21 When pH = 7-10, it assembles into DH-CA. 31 .

[0045] In addition, such as Figure 2 As shown, the present invention also provides a method for preparing a selective fluorite flotation collector, comprising the following steps:

[0046] Step S10: Mix the organic compound containing an amine group, the organic compound containing a deprotonable group, and water to obtain a mixed solution;

[0047] Step S20: The mixed solution is subjected to ultrasonic treatment, and the pH value is adjusted after heating and stirring to obtain a selective fluorite flotation collector.

[0048] In this embodiment, an organic compound containing a deprotonable group is used as a pseudo-gemini surfactant. Based on the electrostatic interaction between its spacer group and two-terminal groups, it pairs with an amine-containing organic compound serving as the surfactant. This synthesis is simple and possesses switchable interfacial activity when external stimuli are introduced. Furthermore, by utilizing electrostatic attraction, selective fluorite flotation collectors with different molar ratios can be assembled by adjusting the pH value. Under neutral and acidic conditions, the collector successfully assembles, forming a pseudo-gemini structure, enhancing the hydrophobicity of the mineral surface, enabling efficient collection of fluorite at low concentrations, increasing concentrate yield, and achieving the purpose of roughing. Under alkaline conditions, the collector decouples into a single molecule of an amine-containing organic compound and an anionic form of an organic compound containing a deprotonable group. The amine-containing organic compound continues to collect fluorite, while the anionic form of the deprotonated organic compound reacts with calcite, reducing the active sites on the calcite surface, inhibiting calcite flotation, improving mineral selectivity, enhancing fluorite flotation recovery, improving separation efficiency, and achieving the purpose of fine cleaning.

[0049] In some embodiments, the molar ratio of the amine-containing organic compound to the organic compound containing the deprotonable group is (1-4):1. By controlling the molar ratio of the raw materials within the above range, selective fluorite flotation collectors with different molar ratios can be prepared according to actual needs.

[0050] In some embodiments, the heating and stirring treatment is performed at a temperature of 50°C-60°C for 30-60 minutes; the pH value is between 5 and 7. By using heating and stirring to increase the reaction rate between the raw materials, followed by pH adjustment, protonated amine-containing organic compounds and deprotonated organic compounds can be electrostatically bonded to form pseudo-gemini surfactants.

[0051] Finally, when the pH value is adjusted to 10-12, the pseudo-gemini structure of the selective fluorite flotation collector gradually disappears, and the solution exists in the form of monomolecular amine-containing organic ions or molecules and anionic forms of organic compounds containing deprotonated groups.

[0052] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention.

[0053] Example 1

[0054] This embodiment provides a selective fluorite flotation collector, DH-CA. xy And fluorite flotation methods, specifically including the following:

[0055] 1) Selective fluorite flotation collector DH-CA xy Preparation

[0056] S10: Weigh 0.2218g of dodecaneamine hydrochloride (DH) and dissolve it in 50mL of deionized water;

[0057] S20: Weigh 0.0961g of citric acid (CA) into S10 solution;

[0058] S30: Sonicate the S20 mixture for 30 minutes to remove air bubbles and promote uniform mixing.

[0059] S40: Place the sonicated solution of S30 on a magnetic stirrer, control the temperature at 50℃, the stirring speed at 1200rpm, and the time at 30min.

[0060] S50: Take out the fully reacted S40 solution, adjust the pH value, and obtain 1×10⁻⁶ solution. -2 A novel pH-responsive switchable collector (DH-CA) at mol / L xy ).

[0061] By utilizing electrostatic attraction and adjusting the pH value in step S50, DH-CA with different molar ratios can be assembled. xy , where x represents the molar number of dodecylammonium ions and y represents the molar number of citric acid. Figure 3 DH-CA was presented xy The structural diagram shows that when 2.6 < pH < 4.3, 1 mol C6H7O7 - With 1 mol C 12 H 25 NH3 + Combine to form DH-CA 11 When pH < 6.5, 1 mol C6H6O7 2- -with 2mol C 12 H 25 NH3 + Combine to form DH-CA 21 When pH < 10.6, 1 mol C6H5O7 3- With 3mol C 12 H 25 NH3 + Combine to form DH-CA 31 At pH > 10.6, dodecaneamine hydrochloride is completely deprotonated to dodecaneamine and cannot react with C6H5O7. 3- Pairing to generate DH-CA xy .

[0062] 2) Based on DH-CA 21The fluorite flotation method, the flotation flow chart is as follows: Figure 4 As shown, the specific steps are as follows:

[0063] i) Single mineral flotation experiment

[0064] The single-mineral flotation samples were pure CaF2 and CaCO3 minerals. The flotation experiments were conducted using an XFGⅡ-5-35g aerated XFG hanging-cell flotation machine manufactured by Wuhan Machinery Exploration Plant. Each experiment used 2.5g of mineral sample, with a flotation concentration of 5% and a rotation speed of 1600-1800 rpm. After stirring the slurry for 3 minutes, the target pH value was adjusted to 5-7 using a pH adjuster, and sodium hexametaphosphate (NaPO3)6 (5×10⁻⁶) was added as an inhibitor. -5 Stir for 2 minutes (mol / L), then add the collector DH-CA. 21 Stir for 2 minutes, then add frother MIBC (50 g / t) and stir for another 2 minutes. Perform aerated flotation for 3 minutes at an aeration rate of 300 mL / min. After flotation, collect the froth product (concentrate) and the product in the tank (tailings), filter, dry, and weigh them separately, and calculate the concentrate recovery rate. Single mineral flotation recovery ε s The calculation is as shown in equation (1):

[0065]

[0066] Where: m c For concentrate quality (g), m t The value represents the tailings mass (g).

[0067] Calculations show that the collector DH-CA 21 The effect of DH concentration on the recovery rates of CaF2 and CaCO3 in single mineral flotation is as follows: Figure 5 As shown. Adjust the pulp pH to 6, when DH-CA 21 Concentration of 5×10 -5 At a concentration of mol / L, the fluorite concentrate recovery rate is 90%, requiring a dosage of 1×10 mol / L compared to the unimolecular collector DH. -4 A concentration of mol / L is needed to achieve a similar effect. Meanwhile, calcite flotation shows similar results, but the overall concentrate recovery rate is lower than that of fluorite. This indicates that DH-CA... xy The collector possesses a pseudo-gemini structure. Compared to traditional collectors, this type of collector exhibits an extremely low critical micelle concentration (CMC), high solubilization capacity, and good wetting and foaming properties. It can significantly reduce the surface tension of water and the oil-water interfacial tension, thereby achieving efficient separation of fluorite and calcite and reducing the amount of flotation reagents required. Under alkaline conditions, DH-CA... xy The released citrate anions from decoupling can inhibit calcite flotation, reduce the amount of traditional inhibitor sodium hexametaphosphate used, and lower flotation costs.

[0068] ii) Flotation experiments of artificially mixed minerals

[0069] CaF2 was separated from the mixed minerals using direct flotation. 2.5 g of a mixed sample of CaF2 and CaCO3 (mass ratio 1:1) was weighed and placed in an XFGⅡ-5-35g aerated XFG hanging tank flotation machine. 50 mL of deionized water was added, the flotation concentration was 5%, and the flotation machine speed was 1600-1800 rpm. First, roughing was performed. After stirring for 3 minutes, pH was adjusted to 5-7 with pH adjuster HCl, sodium hexametaphosphate (NaPO3) inhibitor, and collector DH-CA were added sequentially. 21 Add MIBC frother, open the aeration valve, adjust the aeration rate to 300 mL / min, manually scrape the bubbles for 3 minutes, and collect the roughing concentrate and tailings products. During the cleaning process, adjust the pH of the flotation pulp to 10-12 using NaOH, stir for 3 minutes, then open the aeration valve and manually scrape the bubbles for 3 minutes. Collect the cleaned concentrate and middlings products, filter, dry, and weigh them separately, and calculate and analyze the CaF2 grade in the concentrate and tailings. Mixed mineral recovery ε m The calculation is as shown in equation (2):

[0070]

[0071] Where: m c For concentrate quality (g), β c Concentrate grade (%); m t For tailings mass (g), β t The grade of the tailings is expressed as (%).

[0072] In summary, this invention provides a selective fluorite flotation collector and its preparation method. The selective fluorite flotation collector is formed by electrostatic bonding of an organic compound containing a protonated amine group and an organic compound containing a deprotonated group; wherein the general structural formula of the organic compound containing the protonated amine group is R. + —(CH2) m CH3, R + It is a protonated amino group, (CH2) m CH3 is a hydrophobic chain, m = 12-18; the general structural formula of the anionic organic compound containing the deprotonated group is [Core]-(X - ) n Core is the central framework, X -The term "n" refers to a deprotonated group, where n ≥ 2. This invention utilizes organic compounds containing protonated amine groups and organic compounds containing deprotonated groups to synthesize a selective fluorite flotation collector through electrostatic pairing. Under neutral and acidic conditions, the collector successfully assembles, forming a pseudo-gemini structure, enhancing the hydrophobicity of the mineral surface. This enables efficient collection of fluorite at low concentrations, increasing concentrate yield and achieving the purpose of roughing. Under alkaline conditions, the collector decouples into anionic forms of single-molecule organic compounds containing amine groups and organic compounds containing deprotonated groups. The amine-containing organic compounds continue to collect fluorite, while the anionic form of the deprotonated organic compounds reacts with calcite, reducing active sites on the calcite surface, inhibiting calcite flotation, improving mineral selectivity, enhancing fluorite flotation recovery, increasing separation efficiency, and achieving the purpose of fine cleaning.

[0073] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A selective fluorite flotation collector, characterized in that, formed by electrostatic combination of an organic matter containing protonated amine group and an organic matter containing deprotonated group; wherein the structure general formula of the organic matter containing protonated amine group is R + —(CH2) m CH3, R + is a protonated amine group, (CH2) m CH3is a hydrophobic chain, m = 12-18, and m is an integer; The structure general formula of the organic matter containing deprotonated group is [Core]-(X - ) n , Core is a central skeleton, X - is a deprotonated group, n≥2, and n is an integer.

2. The selective fluorite flotation collector according to claim 1, characterized in that, The protonated amine group includes -NH3 + , -NH2 + , -N + one or more of (CH3)3.

3. The selective fluorite flotation collector according to claim 1, characterized in that, The deprotonated group comprises one or more of -COO - , -SO3 - .

4. The selective fluorite flotation collector according to claim 1, characterized in that, The central skeleton comprises at least one of C2-C10 alkyl, benzene ring, cyclohexane.

5. The selective fluorite flotation collector of claim 1, wherein, The organic matter containing protonated amine group is selected from at least one of protonated dodecylamine hydrochloride, protonated hexadecylamine hydrochloride, protonated hexadecyltrimethylammonium bromide.

6. The selective fluorite flotation collector of claim 1, wherein, The organic matter containing deprotonated group is selected from at least one of deprotonated citric acid, deprotonated oxalic acid, deprotonated ethylenediaminetetraacetic acid, deprotonated 1,5-naphthalenedisulfonic acid.

7. The selective fluorite flotation collector of claim 1, wherein, The molar ratio of the organic matter containing protonated amine group to the organic matter containing deprotonated group is (1-4):

1.

8. A process for the preparation of a selective fluorite flotation collector as claimed in any one of claims 1 to 7, characterised in that, The method comprises the steps of: Mixing an organic matter containing amine group, an organic matter containing deprotonatable group and water to obtain a mixed solution; Ultrasonic treatment is performed on the mixed solution, and the pH value is adjusted after heating and stirring treatment to obtain a selective fluorite flotation collector.

9. The method of producing a selective fluorite flotation collector according to claim 8, characterized in that, The molar ratio of the organic matter containing amine group to the organic matter containing deprotonatable group is (1-4):

1.

10. The method of preparation of a selective fluorite flotation collector according to claim 8, characterized in that, The temperature of the heating and stirring treatment is 50-60°C, and the time of the heating and stirring treatment is 30-60 min; and the pH value is between 5 and 7.

Images