Preparation method of fluorite flotation collector based on mineral gene identification and application thereof

Abstract

The present application belongs to the technical field of mineral processing, and particularly relates to a preparation method of fluorite flotation collector based on mineral gene identification and application thereof. The present application introduces ethylenediamine amide group, p-phenylenediamine rigid skeleton and thiourea group on the molecular skeleton of vegetable oil in three steps, to form a target collector molecule containing primary amine group and thiourea group, wherein the amount of thiourea can be dynamically adjusted according to the type of gangue minerals in fluorite ore. The present application also provides the application of the collector, which dynamically adjusts the reagent system according to the characteristics of fluorite genes, and the compounding ratio of the collector with the main collector and the amount of non-polar hydrocarbon oil are dynamically controlled according to the type of gangue. The present application introduces the "fluorine site recognition" mechanism into the design of fluorite collector for the first time, breaks through the technical bottleneck of traditional "calcium site competition", realizes the precise adaptation of "mineral strategy", and can realize the efficient separation of silicate type, carbonate type and iron-containing rare earth tailing type fluorite ore at low temperature.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing technology, specifically relating to a method for preparing a fluorite flotation collector based on mineral gene recognition and its application. Background Technology

[0002] Fluorite often occurs in close association with various gangue minerals during mineralization. The diverse components of different ores contribute to their unique genetic characteristics, leading to vastly different levels of difficulty in natural separation. Silicate-type fluorite deposits have a high quartz content, making flotation relatively easy; in carbonate-type fluorite deposits, both calcite and fluorite are primarily composed of Ca. 2+ As the main active sites, the flotation responses tend to converge, making selective separation difficult. In iron-rare earth tailings-type fluorite deposits, the associated iron minerals and residual rare earth minerals further exacerbate the separation difficulty, making it difficult to exceed 90% concentrate grade under conventional reagent systems. The surface chemical properties of different types of gangue minerals vary significantly, posing differentiated requirements for the functional group types, adsorption strength, and spatial configuration of collectors.

[0003] However, the design of traditional fatty acid harvesters has long been limited to a static molecular paradigm of "calcium site competition." Conventional agents, such as oleic acid, work by interacting with calcium groups through the carboxyl group. 2+ Non-specific coordination enables adsorption, resulting in a rigid molecular structure. The adsorption process relies on temperature to overcome the activation energy barrier, leading to a sharp decrease in recovery rate at low temperatures. Furthermore, the single functional group structure cannot adapt to the spatiotemporal heterogeneity of active sites on different gangue mineral surfaces. In carbonate ores, it exhibits insufficient selectivity for calcite, and in iron-rare earth tailings ores, it struggles to suppress iron mineral interference, rendering the "one agent, multiple uses" approach ineffective in complex mineralization systems. While traditional inhibition systems such as water glass can shield the Si-O active groups on the quartz surface, they are ineffective against Ca... 2+ The chemical recognition ability of the sites is limited, and it cannot break through the separation efficiency threshold of high-calcium fluorite ore. Foam "dropping" often occurs in the beneficiation process, resulting in poor process stability.

[0004] Research has shown that the essential difference between fluorite and calcite lies in the unique F-type anion-fluorite surface. - It is an extremely strong hydrogen bond acceptor, while gangue minerals such as calcite lack this active site on their surface. Based on this difference, the specific recognition of functional groups and anions can overcome the technical bottleneck of traditional calcium site competition. Therefore, based on the genetic characteristics of fluorite minerals, developing a collector that can dynamically adjust the functional group structure according to the gangue mineral type to achieve precise "mineral-specific" adaptation is of great significance for breaking through the traditional static molecular design paradigm and improving the sorting efficiency of complex fluorite minerals. Summary of the Invention

[0005] The technical problem to be solved by this invention is that traditional fluorite collectors, due to their long-term limitation to the static molecular design paradigm of "calcium site competition", suffer from a series of problems, including insufficient selective recognition ability for different gangue mineral types, sharp reduction in recovery rate under low temperature conditions, difficulty in controlling foam stability, and failure of the "one agent for multiple uses" mode in complex mineralization systems. This invention provides a method for preparing a fluorite flotation collector based on mineral gene recognition. In addition, this invention also provides its application.

[0006] The preparation method of the fluorite flotation collector based on mineral gene recognition described in this invention comprises the following steps:

[0007] (1) Amide reaction: Mix vegetable oil with ethylene glycol, heat to 60-80℃, add ethylenediamine, then raise the temperature to 140-160℃ and keep it at that temperature for 3-5 hours. Remove the generated water through a reflux condenser to obtain fatty acyl ethylenediamine intermediate;

[0008] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) is cooled to 80-100℃, and then terephthalic acid is added and reacted for 1-2 hours to obtain the crosslinked modified intermediate;

[0009] (3) Thiourea group introduction: Thiourea is added to the crosslinking modified intermediate prepared in step (2) to modify the functional groups and prepare fluorite flotation collector.

[0010] Wherein: the vegetable oil mentioned in step (1) is one of oleic acid, soybean oil, rapeseed oil and their acidified oils.

[0011] In step (1), the mass of ethylene glycol accounts for 40%-80% of the mass of the vegetable oil.

[0012] In step (1), the mass ratio of vegetable oil to ethylenediamine is 100: 20-40.

[0013] In step (2), the mass ratio of terephthalic acid to vegetable oil in step (1) is 10-25:100.

[0014] In step (3), the reaction temperature is 80-95℃ and the reaction time is 1-2h.

[0015] The amount of thiourea added in step (3) is adjusted according to the type of gangue mineral in the fluorite ore: ① When the gangue mineral is silicate, the mass ratio of thiourea to vegetable oil is 2-5:100; ② When the gangue mineral is carbonate, the mass ratio of thiourea to vegetable oil is 5-20:100; ③ When the gangue mineral is rare earth and magnetic iron, the mass ratio of thiourea to vegetable oil is 10-15:100.

[0016] When the vegetable oil is oleic acid, the chemical equations involved in the preparation method of the fluorite flotation collector based on mineral gene recognition are as follows:

[0017]

[0018] The application of the fluorite flotation collector based on mineral gene recognition described in this invention involves adjusting the flotation reagent regime according to the genetic characteristics of fluorite ore, and consists of the following steps:

[0019] Fluorite ore is ground to a density of -0.074 mm (50%-95%). A pH adjuster is added to adjust the pH of the pulp to 8-10. Gangue inhibitor, a mixture of fluorite flotation collector based on mineral gene recognition and main collector, and non-polar hydrocarbon oil are added sequentially. After one roughing, multiple cleaning and scavenging processes, fluorite concentrate and tailings are obtained.

[0020] in:

[0021] The mass ratio of the fluorite flotation collector based on mineral gene recognition to the main collector is determined according to the type of gangue minerals in the fluorite ore: ① When the gangue minerals are silicates, the mass ratio of the fluorite flotation collector based on mineral gene recognition to the main collector is 10:90 ~ 20:80; ② When the gangue minerals are carbonates, the mass ratio of the fluorite flotation collector based on mineral gene recognition to the main collector is 30:70 ~ 40:60; ③ When the gangue minerals are rare earth elements and magnetic iron, the mass ratio of the fluorite flotation collector based on mineral gene recognition to the main collector is 20:80 ~ 30:70.

[0022] The non-polar hydrocarbon oil is kerosene or diesel oil. The amount of non-polar hydrocarbon oil added is determined according to the type of gangue minerals in the fluorite ore: ① When the gangue minerals are silicates, the mass of the non-polar hydrocarbon oil is 0-5% of the mass of the compound mixture of fluorite flotation collector and main collector based on mineral gene recognition; ② When the gangue minerals are carbonates, the mass of the non-polar hydrocarbon oil is 5-12% of the mass of the compound mixture of fluorite flotation collector and main collector based on mineral gene recognition; ③ When the gangue minerals are rare earth elements and magnetic iron, the mass of the non-polar hydrocarbon oil is 5-8% of the mass of the compound mixture of fluorite flotation collector and main collector based on mineral gene recognition.

[0023] In the application of the mineral gene recognition-based fluorite flotation collector, the mass concentration of the flotation pulp is 25%~40%, and the pH adjuster is sodium carbonate; the gangue inhibitor is one or more of water glass, carboxymethyl cellulose, tannin, or acidified water glass, with a dosage of 500-2000 g / t; the main collector is one or more of sodium oleate, oleic acid, or tall oil, with a dosage of 200-1000 g / t; the scavenging operation is supplemented with a compound mixture of the mineral gene recognition-based fluorite flotation collector and the main collector, as well as non-polar hydrocarbon oil. The dosage of the compound mixture of the mineral gene recognition-based fluorite flotation collector and the main collector is 1 / 4~1 / 2 of that in the previous operation, and the dosage of the non-polar hydrocarbon oil is 1 / 4~1 / 2 of that in the previous operation; the cleaning operation is supplemented with gangue inhibitor, with a dosage of 1 / 4~1 / 2 of that in the previous operation.

[0024] Compared with the prior art, the present invention has the following advantages:

[0025] (1) The preparation method of the fluorite flotation collector based on mineral gene recognition described in this invention achieves multi-level functional integration of the collector molecule through a three-step stepwise reaction molecular structure design, enabling a single molecule to simultaneously possess the triple functions of fluorine site recognition, steric hindrance amplification, and hydrophobic collection, breaking through the technical limitations of traditional single-functional group collectors with single function and insufficient selectivity. First, a basic framework is constructed using vegetable oil and ethylenediamine as raw materials, so that one amino group of ethylenediamine undergoes selective amidation with fatty acid to form a hydrophobic tail chain, while the other amino group is retained as an active anchor point for subsequent reactions. This design not only ensures hydrophobic performance but also reserves sites for precise expansion of the molecular structure. Then, terephthalic acid is introduced for cross-linking reaction, embedding the rigid benzene ring of terephthalic acid into the molecular framework. Its rigid structure amplifies the subtle differences in the spatial geometry of calcium sites on the surface of fluorite and calcite, enabling the collector molecule to selectively repel calcite through steric hindrance effect. Finally, the collector is endowed with bidentate hydrogen bond recognition function by introducing thiourea groups, utilizing the two NH bonds in the thiourea molecule and the F on the fluorite surface. - The strong hydrogen bonds formed enable the specific capture of target minerals. The three-step reaction is progressive and complementary, ensuring the directional alignment of molecules through the hydrophobic tail chain, amplifying the differences on the mineral surface through the rigid framework, and enabling the thiourea group to achieve specific recognition of target sites. Together, these three elements constitute an intelligent collecting molecule that integrates localization, recognition, and anchoring, fundamentally breaking through the technical barriers of traditional collectors that rely on a single functional group and are unable to achieve multiple functions.

[0026] (2) The application of the fluorite flotation collector based on mineral gene recognition described in this invention proposes for the first time a new molecular design mechanism for fluorite collectors based on "fluorine site recognition," breaking through the technical bottleneck of traditional "calcium site competition." Traditional fatty acid collectors rely on the interaction of carboxyl groups with Ca... 2+Adsorption is achieved through nonspecific coordination between fluorite and calcite surfaces, due to the Ca2+ adsorption. 2+ The similarity in flotation sites makes it difficult to distinguish the flotation responses of the two materials. This invention is based on the unique F-type flotation sites on the surface of fluorite. - Due to the fundamental difference that calcite and other gangue rocks lack this active site, a double hydrogen bond donor structure containing primary amine and thiourea groups was designed and synthesized. This structure allows for the bonding of the primary amine group with F... - The synergistic effect of monodentate hydrogen bonds and bidentate hydrogen bonds of thiourea groups enables highly selective identification of fluorite, fundamentally solving the industry problem of selective separation of fluorite from calcium-containing gangue minerals.

[0027] (3) The application of the fluorite flotation collector based on mineral gene recognition described in this invention establishes a dynamic regulation mechanism for functional group density based on the gene characteristics of fluorite ore, achieving precise adaptation between the collector molecular structure and the spatiotemporal heterogeneity of active sites on the gangue mineral surface. Different types of fluorite ore exhibit significant differences in gangue mineral composition and surface chemical properties, posing differentiated requirements for the type, density, and spatial arrangement of functional groups in the collector. This invention, by directionally regulating the introduction of thiourea groups, enables the density of bidentate hydrogen bond donors in the collector molecule to be dynamically adjusted according to different ore types such as silicate type, carbonate type, and iron-rare earth tailings type, thereby achieving optimal matching with the distribution characteristics of active sites on the surface of various gangue minerals. This functional group density regulation strategy based on mineral gene characteristics allows the collector molecule to respond in an "adaptive" manner to the spatiotemporal evolution of mineral surface properties under different mineralization environments, breaking through the technical bottleneck of traditional collectors that struggle to accommodate multiple ore types due to fixed functional group density.

[0028] (4) This invention establishes a dynamic control mechanism for the ratio of the collector to the main collector, achieving a synergistic effect between the fluoride site recognition function and the hydrophobic collection function. The collector, based on its ability to detect fluoride sites on the fluorite surface, [is effective]. - The specific recognition capability of the collector preferentially marks the active sites on the surface of the target mineral, providing precise "navigation" for the subsequent adsorption of the main collector. The main collector, with its strong hydrophobic properties, forms a dense coating layer around the marked sites. The two form an ordered mixed adsorption structure on the mineral surface. By adjusting the ratio of the two, the recognition and collection functions are optimized in different types of ores, ensuring both the selective marking efficiency of the collector on fluorite and the sufficient hydrophobic coating of the main collector on the target mineral. This avoids the inefficient mode of mutual interference or simple superposition of the functions of the components in traditional compound systems.

[0029] (5) This invention establishes a dynamic control mechanism for the amount of non-polar hydrocarbon oil added, achieving precise matching between flotation foam performance and ore type. Non-polar hydrocarbon oil regulates the stability, dispersibility, and ore-carrying capacity of foam by forming a molecular-level oil film on the bubble surface, and its effect is non-linearly related to the amount added. This invention establishes a dynamic control strategy for the amount of hydrocarbon oil added to meet the differentiated requirements of different types of gangue minerals for foam performance, enabling foam performance to adaptively optimize with changes in ore properties. This fundamentally solves the process problems under traditional reagent systems, such as the difficulty in meeting the needs of multiple types of ores in terms of foam performance, and the easy occurrence of "dropping" or excessively sticky foam in the beneficiation process.

[0030] (6) This invention constructs a four-level linkage control system of "mineral type-functional group density-reagent ratio-process parameters" through multi-level functional integration of the collector molecular structure, dynamic regulation of functional group density, synergistic optimization of compound ratio, and precise adaptation of hydrocarbon oil dosage. This enables the reagent system to adapt to the spatiotemporal heterogeneity of active sites on the surface of different gangue minerals, achieving a fundamental leap from static molecular design to dynamic response regulation. This technology not only provides a new technical paradigm for the efficient and low-carbon separation of complex fluorite ores, but can also be extended to calcium-containing mineral systems such as scheelite, phosphate rock, and rare earth minerals, demonstrating good technical universality and application value. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the preparation method of the fluorite flotation collector based on mineral gene recognition according to the present invention;

[0032] Figure 2 This is a flowchart illustrating the application principles of the mineral gene recognition-based fluorite flotation collector described in this invention in the flotation separation of carbonate, rare earth tailings, and silicate fluorite ores.

[0033] Figure 3 The nuclear magnetic resonance spectrum of the fluorite flotation collector based on mineral gene recognition prepared in Example 2 of this invention;

[0034] Figure 4 The infrared spectrum is shown for the fluorite flotation collector based on mineral gene recognition prepared in Example 2 of this invention. Detailed Implementation

[0035] Example 1

[0036] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Example 1 consists of the following steps:

[0037] (1) Amide reaction: 100 parts of soybean acidified oil were added to the reaction vessel, 60 parts of ethylene glycol were added, and the mixture was stirred and heated to 70°C. Then 25 parts of ethylenediamine were added, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 150°C and the reaction was kept at the temperature for 4 hours. During the reaction, the generated water was continuously removed through a reflux condenser to obtain fatty amide ethylenediamine intermediate.

[0038] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 90°C, 15 parts of terephthalic acid were added, and the mixture was stirred at 90°C for 1.5 hours to obtain the crosslinked modified intermediate.

[0039] (3) Thiourea group introduction: 10 parts of thiourea were added to the crosslinking modified intermediate prepared in step (2), and the mixture was stirred at 90°C for 1.5 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a fluorite flotation collector based on mineral gene recognition.

[0040] A carbonate-type fluorite ore from Inner Mongolia was used, with a raw ore CaF2 grade of 30.15% and a calcite content of 21.53%. The ore was ground to a particle size of -0.074 mm (85%), and the pulp concentration was adjusted to 40%. Sodium carbonate was then added to adjust the pulp pH to 9, followed by the addition of 1000 g / t of water glass as a depressant. After thorough mixing, a mixture of the mineral gene recognition-based fluorite flotation collector and sodium oleate prepared in Example 1 was added, with a mass ratio of 40:60 (total dosage 700 g / t). Non-polar hydrocarbon oil (kerosene) was also added, amounting to 12% (84 g / t) of the total mixture of the mineral gene recognition-based fluorite flotation collector and the main collector. Fluorite concentrate was obtained through one roughing, seven cleaning, and two scavenging processes. In the first to fourth refinement operations, acidified water glass was added as an inhibitor at dosages of 500 g / t, 200 g / t, 100 g / t, and 50 g / t, respectively. No reagent was added in refinement operations V, VI, and VII. In scavenging operations I and II, 300 g / t and 200 g / t of the compound mixture of fluorite flotation collector and main collector prepared in Example 1 based on mineral gene recognition, and 40 g / t and 20 g / t of kerosene were added, respectively. Fluorite concentrate and tailings were obtained by flotation in slurry at 15°C.

[0041] Comparative Example 1

[0042] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 1 consists of the following steps:

[0043] (1) Amide reaction: 100 parts of soybean acidified oil were added to the reaction vessel and heated to 70°C. 25 parts of ethylenediamine were added directly, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 150°C and kept warm for 4 hours. The water generated during the reaction was not removed, and crude fatty ethylenediamine intermediate was obtained.

[0044] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 90°C, 15 parts of terephthalic acid were added, and the mixture was stirred at 90°C for 1.5 hours to obtain the crosslinked modified intermediate.

[0045] (3) Thiourea group introduction: Add 10 parts of thiourea to the crosslinking modified intermediate prepared in step (2), stir and react at 90°C for 1.5 hours, and cool to room temperature after the reaction to obtain the collector.

[0046] The application of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 1 is the same as that in Example 1, except that the fluorite flotation collector is prepared using the method of Comparative Example 1.

[0047] Comparative Example 2

[0048] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 2 consists of the following steps:

[0049] (1) Crosslinking reaction: 100 parts of soybean acidified oil were added to the reaction vessel, 60 parts of ethylene glycol were added, the mixture was stirred and mixed evenly, and then heated to 90°C. 15 parts of terephthalic acid were added, and the mixture was stirred at 90°C for 1.5 hours to obtain a crosslinking intermediate mixture.

[0050] (2) Thiourea group introduction: Add 10 parts of thiourea to the crosslinking intermediate mixture prepared in step (1), stir and react at 90°C for 1.5 hours, and cool to room temperature after the reaction to obtain the collector product.

[0051] The application of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 2 is the same as that in Example 1, except that the fluorite flotation collector is prepared using the method of Comparative Example 2.

[0052] Comparative Example 3

[0053] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 3 consists of the following steps:

[0054] (1) Amide reaction: 100 parts of soybean acidified oil were added to the reaction vessel, 60 parts of ethylene glycol were added, and the mixture was stirred and heated to 70°C. Then 25 parts of ethylenediamine were added, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 150°C and the reaction was kept at the temperature for 4 hours. During the reaction, the generated water was continuously removed through a reflux condenser to obtain fatty amide ethylenediamine intermediate.

[0055] (2) Introduction of thiourea group: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 90°C, and 10 parts of thiourea were added directly. The mixture was stirred at 90°C for 1.5 hours. After the reaction was completed, it was cooled to room temperature to obtain the collector.

[0056] The application of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 3 is the same as that in Example 1, except that the fluorite flotation collector is prepared using the method of Comparative Example 3.

[0057] Comparative Example 4

[0058] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 4 consists of the following steps:

[0059] (1) Amide reaction: 100 parts of soybean acidified oil were added to the reaction vessel, 60 parts of ethylene glycol were added, and the mixture was stirred and heated to 70°C. Then 25 parts of ethylenediamine were added, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 150°C and the reaction was kept at the temperature for 4 hours. During the reaction, the generated water was continuously removed through a reflux condenser to obtain fatty amide ethylenediamine intermediate.

[0060] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 90°C, 15 parts of terephthalic acid were added, and the mixture was stirred at 90°C for 1.5 hours. After the reaction was completed, it was cooled to room temperature to obtain the collector.

[0061] The application of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 4 is the same as that in Example 1, except that the fluorite flotation collector is prepared using the method of Comparative Example 4.

[0062] Comparative Example 5

[0063] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 5 consists of the following steps:

[0064] (1) Amide reaction: 100 parts of soybean acidified oil were added to the reaction vessel, 60 parts of ethylene glycol were added, and the mixture was stirred and heated to 70°C. Then 25 parts of ethylenediamine were added, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 150°C and the reaction was kept at the temperature for 4 hours. During the reaction, the generated water was continuously removed through a reflux condenser to obtain fatty amide ethylenediamine intermediate.

[0065] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 90°C, 15 parts of terephthalic acid were added, and the mixture was stirred at 90°C for 1.5 hours to obtain the crosslinked modified intermediate.

[0066] (3) Thiourea group introduction: Add 3 parts of thiourea to the crosslinking modified intermediate prepared in step (2), stir and react at 90°C for 1.5 hours, and cool to room temperature after the reaction to obtain fluorite flotation collector based on mineral gene recognition.

[0067] The application of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 5 is the same as that in Example 1, except that the fluorite flotation collector is prepared using the method of Comparative Example 5.

[0068] Comparative Example 6

[0069] This application example uses a carbonate-type fluorite mine in Inner Mongolia. The raw ore has a CaF2 grade of 30.15% and a calcite content of 21.53%. The ore is ground to a particle size of -0.074 mm (85%), and the pulp concentration is adjusted to 40%. Sodium carbonate is then added to adjust the pulp pH to 9, followed by 1000 g / t of water glass as a depressant. After thorough mixing, a mixture of the mineral gene recognition-based fluorite flotation collector and sodium oleate prepared in Example 1 is added, with a mass ratio of 20:80 (total dosage 700 g / t). Non-polar hydrocarbon oil (kerosene) is also added at 12% of the total amount of the mixture of the mineral gene recognition-based fluorite flotation collector and the main collector, i.e., 84 g / t. Fluorite concentrate is obtained after one roughing, seven cleaning, and two scavenging processes. In the first to fourth refinement operations, acidified water glass was added as an inhibitor at dosages of 500 g / t, 200 g / t, 100 g / t, and 50 g / t, respectively. No reagent was added in refinement operations V, VI, and VII. In scavenging operations I and II, 300 g / t and 200 g / t of the compound mixture of fluorite flotation collector and main collector prepared in Example 1 based on mineral gene recognition, and 40 g / t and 20 g / t of kerosene were added, respectively. Fluorite concentrate and tailings were obtained by flotation in slurry at 15°C.

[0070] Comparative Example 7

[0071] This application example uses a carbonate-type fluorite mine in Inner Mongolia. The raw ore has a CaF2 grade of 30.15% and a calcite content of 21.53%. The ore is ground to a particle size of -0.074 mm (85%), and the pulp concentration is adjusted to 40%. Sodium carbonate is then added to adjust the pulp pH to 9, followed by 1000 g / t of water glass as a depressant. After thorough mixing, a mixture of collector and sodium oleate prepared in Example 1 is added, with a collector-to-sodium oleate mass ratio of 40:60 and a total dosage of 700 g / t. Non-polar hydrocarbon oil (kerosene) is also added at 3% of the total dosage of the mixture of fluorite flotation collector and main collector based on mineral gene recognition, i.e., 21 g / t. Fluorite concentrate is obtained after one roughing, seven cleaning, and two scavenging processes. In the first to fourth refinement operations, acidified water glass was added as an inhibitor at dosages of 500 g / t, 200 g / t, 100 g / t, and 50 g / t, respectively. No reagent was added in refinement operations V, VI, and VII. In scavenging operations I and II, 300 g / t and 200 g / t of the compound mixture of fluorite flotation collector and main collector prepared in Example 1 based on mineral gene recognition, and 10 g / t and 5 g / t of kerosene were added, respectively. Fluorite concentrate and tailings were obtained by flotation in slurry at 15°C.

[0072] Comparative Example 8

[0073] This application example uses a carbonate-type fluorite mine in Inner Mongolia. The raw ore has a CaF2 grade of 30.15% and a calcite content of 21.53%. The ore is ground to a particle size of -0.074 mm (85%), and the pulp concentration is adjusted to 40%. Sodium carbonate is then added to adjust the pulp pH to 9, followed by the addition of 1000 g / t of water glass as a depressant. After thorough mixing, sodium oleate collector is added at a dosage of 700 g / t. Fluorite concentrate is obtained through one roughing, seven cleaning, and two scavenging processes. Acidified water glass is added as a depressant in Cleaning I to Cleaning IV, at dosages of 500 g / t, 200 g / t, 100 g / t, and 50 g / t, respectively. No reagent is added in Cleaning V, Cleaning VI, and Cleaning VII. Sodium oleate is added at 300 g / t and 200 g / t in Scavenging I and Scavenging II, respectively. Fluorite concentrate and tailings are obtained by flotation.

[0074] Comparative Example 9

[0075] This application example uses a carbonate-type fluorite mine in Inner Mongolia. The raw ore has a CaF2 grade of 30.15% and a calcite content of 21.53%. The ore is ground to a particle size of -0.074 mm (85%), and the pulp concentration is adjusted to 40%. Sodium carbonate is then added to adjust the pulp pH to 9, followed by the addition of 1000 g / t of water glass as a depressant. After thorough mixing, sodium oleate collector is added at a dosage of 700 g / t. Fluorite concentrate is obtained through one roughing, seven cleaning, and two scavenging processes. Acidified water glass is added as a depressant in Cleaning I to Cleaning IV, at dosages of 500 g / t, 200 g / t, 100 g / t, and 50 g / t, respectively. No reagent is added in Cleaning V, Cleaning VI, and Cleaning VII. Sodium oleate is added at 300 g / t and 200 g / t in Scavenging I and Scavenging II, respectively. Flotation is carried out in a 30°C pulp to obtain fluorite concentrate and tailings.

[0076] Example 2

[0077] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Example 2 consists of the following steps:

[0078] (1) Amide reaction: 100 parts of oleic acid were added to the reaction vessel, 40 parts of ethylene glycol were added, and the mixture was stirred and heated to 80°C. Then 40 parts of ethylenediamine were added, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 160°C and the reaction was kept at the temperature for 3 hours. During the reaction, the generated water was continuously removed through a reflux condenser to obtain the fatty amide ethylenediamine intermediate.

[0079] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 100°C, 10 parts of terephthalic acid were added, and the mixture was stirred at 100°C for 2 hours to obtain the crosslinked modified intermediate.

[0080] (3) Thiourea group introduction: 12 parts of thiourea were added to the crosslinking modified intermediate prepared in step (2), and the mixture was stirred at 95°C for 1 hour. After the reaction was completed, the mixture was cooled to room temperature to obtain a fluorite flotation collector based on mineral gene recognition.

[0081] Figure 3The NMR results for the mineral gene recognition-based fluorite flotation collector prepared above show a doublet (d, J = 1.0 Hz) at δ 7.81 with an integral value of 4H, attributed to the aromatic hydrogen on the benzene ring in the terephthalic acid structural unit; a multiplet (m) at δ 3.62–3.52 with an integral value of 45H, mainly corresponding to the hydrogen signal of the methylene group in unreacted ethylene glycol (HO-CH2-CH2-OH); a multiplet (ddd, J = 33.0, 7.1, 4.3 Hz) at δ 3.32 with an integral value of 2H, possibly corresponding to the methylene hydrogen in a small amount of reacted ethylenediamine fragment (-NH-CH2-CH2-NH-); a singlet (s) at δ 2.81 with an integral value of 12H, attributed to the hydrogen signal of the methylene group in unreacted free ethylenediamine (H2N-CH2-CH2-NH2); and a singlet at δ 1.21. A singlet (s) with an integral value of 1H is observed, which may originate from the methylene hydrogen of the aliphatic chain in the trace amount of soluble oligomer. This result demonstrates that the terephthalic acid unit has been successfully introduced into the product structure.

[0082] Figure 4 The infrared results of the mineral gene recognition-based fluorite flotation collector prepared above are shown in Table 1 below:

[0083] Table 1. Infrared results of the fluorite flotation collector based on mineral gene recognition prepared in Example 2.

[0084]

[0085] A rare earth tailings type fluorite ore from Inner Mongolia was used. After magnetic separation to remove iron and rare earth elements, the raw ore had a CaF2 grade of 22.31%, a TFe grade of 5.21%, and a REO content of 7.29%. The ore was ground to a particle size of -0.074 mm (93%), and the pulp concentration was adjusted to 35%. Sodium carbonate was then added to adjust the pulp pH to 10. Subsequently, 1000 g / t of carboxymethyl cellulose and 500 g / t of tannin were added as inhibitors. After stirring evenly, a mixture of fluorite flotation collector based on mineral gene recognition and oleic acid prepared in Example 2 was added, wherein the mass ratio of the fluorite flotation collector based on mineral gene recognition to oleic acid was 25:75, with a total dosage of 1000 g / t. Non-polar hydrocarbon oil diesel was also added at a dosage of 6% of the total dosage of the mixture of fluorite flotation collector based on mineral gene recognition and the main collector, i.e., 60 g / t. Fluorite concentrate was obtained through one roughing, six cleaning, and two scavenging processes. Carboxymethyl cellulose was added as an inhibitor in cleaning processes I to IV, at dosages of 400 g / t, 200 g / t, 100 g / t, and 50 g / t, respectively. No inhibitor was added in cleaning processes V, VI, and VII. In scavenging processes I and II, 400 g / t and 200 g / t of the compound mixture of fluorite flotation collector and main collector prepared in Example 2 based on mineral gene recognition, and 30 g / t and 10 g / t of diesel oil were added, respectively. Flotation was carried out in a low-temperature slurry at 15°C to obtain fluorite concentrate and tailings.

[0086] Comparative Example 10

[0087] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 10 consists of the following steps:

[0088] (1) Amide reaction: 100 parts of oleic acid were added to the reaction vessel, 40 parts of ethylene glycol were added, and the mixture was stirred and heated to 80°C. Then 40 parts of ethylenediamine were added, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 160°C and the reaction was kept at the temperature for 3 hours. During the reaction, the generated water was continuously removed through a reflux condenser to obtain the fatty amide ethylenediamine intermediate.

[0089] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 100°C, 10 parts of terephthalic acid were added, and the mixture was stirred at 100°C for 2 hours to obtain the crosslinked modified intermediate.

[0090] (3) Thiourea group introduction: 20 parts of thiourea were added to the crosslinking modified intermediate prepared in step (2), and the mixture was stirred at 95°C for 1 hour. After the reaction was completed, the mixture was cooled to room temperature to obtain a fluorite flotation collector based on mineral gene recognition.

[0091] The application of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 10 is the same as that in Example 2, except that the fluorite flotation collector is prepared using the method of Comparative Example 10.

[0092] Comparative Example 11

[0093] This application example uses a rare earth tailings type fluorite mine in Inner Mongolia. After magnetic separation to remove iron and rare earth elements, the raw ore has a CaF2 grade of 22.31%, a TFe grade of 5.21%, and a REO content of 7.29%. The ore is ground to a particle size of -0.074 mm (93%), and the pulp concentration is adjusted to 35%. Sodium carbonate is then added to adjust the pulp pH to 10. Subsequently, 1000 g / t of carboxymethyl cellulose and 500 g / t of tannin are added as inhibitors. After stirring evenly, a mixture of fluorite flotation collector based on mineral gene recognition and oleic acid prepared in Example 2 is added, wherein the mass ratio of the fluorite flotation collector based on mineral gene recognition to oleic acid is 10:90, with a total dosage of 1000 g / t. Non-polar hydrocarbon oil diesel is also added at a dosage of 6% of the total dosage of the mixture of fluorite flotation collector based on mineral gene recognition and the main collector, i.e., 60 g / t. Fluorite concentrate was obtained through one roughing, six cleaning, and two scavenging processes. Carboxymethyl cellulose was added as an inhibitor in cleaning processes I to IV, at dosages of 400 g / t, 200 g / t, 100 g / t, and 50 g / t, respectively. No inhibitor was added in cleaning processes V, VI, and VII. In scavenging processes I and II, 400 g / t and 200 g / t of the compound mixture of fluorite flotation collector and main collector prepared in Example 2 based on mineral gene recognition, and 30 g / t and 10 g / t of diesel oil were added, respectively. Flotation was carried out in a low-temperature slurry at 15°C to obtain fluorite concentrate and tailings.

[0094] Comparative Example 12

[0095] This application example uses a rare earth tailings type fluorite mine in Inner Mongolia. After magnetic separation to remove iron and rare earth elements, the raw ore has a CaF2 grade of 22.31%, a TFe grade of 5.21%, and a REO content of 7.29%. The ore is ground to a particle size of -0.074 mm (93%), and the pulp concentration is adjusted to 35%. Sodium carbonate is then added to adjust the pulp pH to 10. Subsequently, 1000 g / t of carboxymethyl cellulose and 500 g / t of tannin are added as inhibitors. After stirring evenly, a mixture of fluorite flotation collector based on mineral gene recognition and oleic acid prepared in Example 2 is added, wherein the mass ratio of the fluorite flotation collector based on mineral gene recognition to oleic acid is 25:75, with a total dosage of 1000 g / t. Non-polar hydrocarbon oil diesel is also added at a dosage of 3% of the total dosage of the mixture of fluorite flotation collector based on mineral gene recognition and the main collector, i.e., 30 g / t. Fluorite concentrate was obtained through one roughing, six cleaning, and two scavenging processes. Carboxymethyl cellulose was added as an inhibitor in cleaning processes I to IV at dosages of 400 g / t, 200 g / t, 100 g / t, and 50 g / t, respectively. No inhibitor was added in cleaning processes V, VI, and VII. In scavenging processes I and II, 400 g / t and 200 g / t of the compound mixture of fluorite flotation collector and main collector prepared in Example 2 based on mineral gene recognition, and 15 g / t and 5 g / t of diesel oil were added, respectively. Flotation was carried out in a low-temperature slurry at 15°C to obtain fluorite concentrate and tailings.

[0096] Comparative Example 13

[0097] This application example uses a rare earth tailings type fluorite mine in Inner Mongolia. After magnetic separation to remove iron and rare earth elements, the raw ore has a CaF2 grade of 22.31%, a TFe grade of 5.21%, and a REO content of 7.29%. The ore is ground to a particle size of -0.074 mm (93%), and the pulp concentration is adjusted to 35%. Sodium carbonate is then added to adjust the pulp pH to 10. Subsequently, carboxymethyl cellulose and tannin (1000 g / t and 500 g / t respectively) are added as depressants. After thorough mixing, oleic acid is added at a dosage of 1000 g / t. Fluorite concentrate is obtained through one roughing process, six cleaning processes, and two scavenging processes. Carboxymethyl cellulose was added as an inhibitor in the first to fourth cleaning operations, with dosages of 400 g / t, 200 g / t, 100 g / t and 50 g / t respectively. No inhibitor was added in cleaning operations V, VI and VII. Oleic acid was added in scavenging operations I and II, respectively, at 400 g / t and 200 g / t. The flotation was carried out in a low-temperature slurry at 15°C to obtain fluorite concentrate and tailings.

[0098] Example 3

[0099] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Example 3 consists of the following steps:

[0100] (1) Amide reaction: 100 parts of rapeseed oil were added to the reaction vessel, 80 parts of ethylene glycol were added, and the mixture was stirred and heated to 60°C. Then 20 parts of ethylenediamine were added, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 140°C and the reaction was kept at the temperature for 5 hours. During the reaction, the generated water was continuously removed through a reflux condenser to obtain fatty amide ethylenediamine intermediate.

[0101] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 90°C, 25 parts of terephthalic acid were added, and the mixture was stirred at 90°C for 2 hours to obtain the crosslinked modified intermediate.

[0102] (3) Thiourea group introduction: Add 3 parts of thiourea to the crosslinking modified intermediate prepared in step (2), stir and react at 80°C for 2 hours, and cool to room temperature after the reaction to obtain fluorite flotation collector based on mineral gene recognition.

[0103] This application example uses a silicate-type fluorite ore from Gansu Province, with a CaF2 grade of 45.13% and a SiO2 grade of 39.25%. The ore is ground to a particle size of -0.074 mm (75%), and the pulp concentration is adjusted to 25%. Sodium carbonate is then added to adjust the pulp pH to 8, followed by the addition of 2000 g / t of water glass as a depressant. After thorough mixing, a mixture of the mineral gene recognition-based fluorite flotation collector and tall oil prepared in Example 3 is added, with a mass ratio of 15:85 (total dosage 400 g / t). Non-polar hydrocarbon diesel oil is also added at 2% of the total mixture (8 g / t). Fluorite concentrate is obtained after one roughing, six cleaning, and two scavenging processes. Water glass was added as an inhibitor in the first to third cleaning operations at dosages of 800 g / t, 300 g / t, and 100 g / t, respectively. No reagent was added in the fourth, fifth, and sixth cleaning operations. In the scavenging operations, 100 g / t and 50 g / t of the compound mixture of fluorite flotation collector and main collector prepared in Example 3 based on mineral gene recognition, as well as 4 g / t and 2 g / t of diesel oil were added, respectively. Flotation was carried out in a low-temperature slurry at 15°C to obtain fluorite concentrate and tailings.

[0104] Comparative Example 14

[0105] The preparation method of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 14 consists of the following steps:

[0106] (1) Amide reaction: 100 parts of rapeseed oil were added to the reaction vessel, 80 parts of ethylene glycol were added, and the mixture was stirred and heated to 60°C. Then 20 parts of ethylenediamine were added, and the temperature was controlled not to exceed 100°C during the feeding process. After the feeding was completed, the temperature was raised to 140°C and the reaction was kept at the temperature for 5 hours. During the reaction, the generated water was continuously removed through a reflux condenser to obtain fatty amide ethylenediamine intermediate.

[0107] (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) was cooled to 90°C, 25 parts of terephthalic acid were added, and the mixture was stirred at 90°C for 2 hours to obtain the crosslinked modified intermediate.

[0108] (3) Thiourea group introduction: 10 parts of thiourea were added to the crosslinking modified intermediate prepared in step (2), and the mixture was stirred at 80°C for 2 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain a fluorite flotation collector based on mineral gene recognition.

[0109] The application of the fluorite flotation collector based on mineral gene recognition described in Comparative Example 14 is the same as that in Example 3, except that the fluorite flotation collector is prepared using the method of Comparative Example 14.

[0110] Comparative Example 15

[0111] This application example uses a silicate-type fluorite ore from Gansu Province, with a CaF2 grade of 45.13% and a SiO2 grade of 39.25%. The ore is ground to a particle size of -0.074 mm (75%), and the pulp concentration is adjusted to 25%. Sodium carbonate is then added to adjust the pulp pH to 8, followed by the addition of 2000 g / t of water glass as a depressant. After thorough mixing, a mixture of the mineral gene recognition-based fluorite flotation collector and tall oil prepared in Example 3 is added, with a mass ratio of 30:70 (total dosage 400 g / t). Non-polar hydrocarbon diesel oil is also added at 2% of the total mixture of the mineral gene recognition-based fluorite flotation collector and the main collector, i.e., 8 g / t. Fluorite concentrate is obtained after one roughing, six cleaning, and two scavenging processes. Water glass was added as an inhibitor in the first to third cleaning operations at dosages of 800 g / t, 300 g / t, and 100 g / t, respectively. No reagent was added in the fourth, fifth, and sixth cleaning operations. In the scavenging operations, 100 g / t and 50 g / t of the compound collector prepared in Example 3, and 4 g / t and 2 g / t of diesel oil were added, respectively. The flotation was carried out in a low-temperature slurry at 15°C to obtain fluorite concentrate and tailings.

[0112] Comparative Example 16

[0113] This application example uses Gansu silicate-type fluorite ore with a CaF2 grade of 45.13% and a SiO2 grade of 39.25%. The ore is ground to a particle size of -0.074 mm (75%), and the pulp concentration is adjusted to 25%. Sodium carbonate is then added to adjust the pulp pH to 8, followed by the addition of 2000 g / t of water glass as a depressant. After thorough mixing, a mixture of the mineral gene recognition-based fluorite flotation collector and tall oil prepared in Example 3 is added. The mass ratio of the prepared mineral gene recognition-based fluorite flotation collector to tall oil is 15:85, with a total dosage of 400 g / t. Non-polar hydrocarbon diesel oil is also added, at 8% of the total dosage of the mixture of the mineral gene recognition-based fluorite flotation collector and the main collector, i.e., 32 g / t. Fluorite concentrate is obtained after one roughing, six cleaning, and two scavenging processes. Water glass was added as an inhibitor in the first to third cleaning operations at dosages of 800 g / t, 300 g / t, and 100 g / t, respectively. No reagent was added in the fourth, fifth, and sixth cleaning operations. In the scavenging operations, 100 g / t and 50 g / t of the compound mixture of fluorite flotation collector and main collector prepared in Example 3 based on mineral gene recognition, as well as 15 g / t and 5 g / t of diesel oil were added, respectively. Flotation was carried out in a low-temperature slurry at 15°C to obtain fluorite concentrate and tailings.

[0114] Comparative Example 17

[0115] This application example uses a silicate-type fluorite ore from Gansu Province, with a CaF2 grade of 45.13% and a SiO2 grade of 39.25%. The ore is ground to a particle size of -0.074 mm (75%), and the pulp concentration is adjusted to 25%. Sodium carbonate is then added to adjust the pulp pH to 8, followed by the addition of 2000 g / t of water glass as a depressant. After thorough mixing, tall oil is added at a dosage of 400 g / t. Fluorite concentrate is obtained through one roughing process, six cleaning processes, and two scavenging processes. Water glass is added as a depressant in Cleaning I to Cleaning III, at dosages of 800 g / t, 300 g / t, and 100 g / t, respectively. No depressant is added in Cleaning IV, Cleaning V, and Cleaning VI. Tall oil is added in Scavenging I and Scavenging II, respectively, and flotation is carried out in a low-temperature pulp at 15°C to obtain fluorite concentrate and tailings.

[0116] The flotation effects of Examples 1-3 and Comparative Examples 1-17 are summarized, and their main flotation indicators are listed in Tables 2-4.

[0117] Table 2. Flotation test results of Example 1 and Comparative Examples 1-9

[0118]

[0119] Table 3. Flotation test results of Example 2 and Comparative Examples 10-13

[0120]

[0121] Table 4. Flotation test results of Example 3 and Comparative Examples 14-17

[0122]

[0123] The data obtained from the flotation tests in Table 1-3 show that:

[0124] (1) In Comparative Example 1, ethylene glycol was not added during the amidation reaction, and the generated water was not removed using a reflux condenser. The absence of ethylene glycol prevented the formation of a homogeneous reaction system, resulting in insufficient contact between the vegetable oil and ethylenediamine. The generated water was not removed in time, causing the amidation reaction equilibrium to shift in the reverse direction. These factors combined to significantly reduce the yield of the fatty amide ethylenediamine intermediate, preventing subsequent cross-linking reactions and the introduction of thiourea groups from proceeding at sufficient active sites, and resulting in an incomplete collector molecular structure. Flotation test results showed that the concentrate CaF2 grade of Comparative Example 1 was 87.29%, and the recovery rate was 83.17%, representing decreases of 10.92 and 8.10 percentage points respectively compared to Example 1. The froth was unstable, and some froth fell off the tank. This indicates that the addition of ethylene glycol not only acts as a reaction solvent to promote a homogeneous reaction but, more importantly, imparts good low-temperature fluidity to the final product. Timely removal of the generated water is crucial for driving the amidation reaction equilibrium to shift in the forward direction and ensuring the reaction proceeds fully.

[0125] (2) Comparative Example 2 omitted the first-step amidation reaction. Instead of reacting ethylenediamine with vegetable oil to construct the fatty acyl ethylenediamine basic skeleton, the vegetable oil was directly cross-linked with terephthalic acid. Because vegetable oil lacks primary amine active sites that can react with terephthalic acid, terephthalic acid could not cross-link with the target site, and the subsequent thiourea group could not be effectively introduced. The resulting product was a simple mixture of vegetable oil, terephthalic acid, and thiourea. Flotation test results showed that the concentrate CaF2 grade of Comparative Example 2 was only 82.31%, and the recovery rate was only 53.12%, a decrease of 15.90 percentage points and 38.15 percentage points respectively compared to Example 1. Furthermore, the product exhibited severe stratification, and flotation could not proceed normally. This indicates that the construction of the fatty acyl ethylenediamine intermediate is fundamental to the entire molecular design. The amide bonds formed through the amidation reaction provide precise chemical anchors for the subsequent introduction of the rigid skeleton and modification of the recognition group; the amidation reaction is indispensable.

[0126] (3) In Comparative Example 3, the cross-linking reaction step was omitted after the amidation reaction was completed, and the rigid benzene ring skeleton of terephthalic acid was not introduced; instead, the thiourea group was directly introduced. Due to the lack of a rigid benzene ring structure, the collector molecule could not amplify the geometrical difference between the calcium sites on the surfaces of fluorite and calcite through steric hindrance. The calcium ions on the (111) face of fluorite form an open platform with a regular triangular array, which is conducive to molecular adsorption; while the calcium ions on the (104) face of calcite are adsorbed by CO3.2- The rigid benzene ring skeleton forms a semi-closed groove, making it difficult for rigid molecules to adsorb stably due to steric hindrance. Without the rigid skeleton, this recognition difference is weakened, resulting in insufficient selective inhibition of calcite. Table 1 shows that the CaF2 grade of the concentrate in Comparative Example 3 was 89.12%, and the recovery rate was 87.11%, which were 9.09 percentage points and 4.16 percentage points lower than those in Example 1, respectively. This indicates that the steric hindrance effect of the rigid benzene ring skeleton is a key factor in achieving selective recognition. Its role is to amplify the microscopic differences on the mineral surface through molecular geometry, enabling the collector molecules to "sense" and "distinguish" the subtle differences in calcium sites on the surfaces of fluorite and calcite.

[0127] (4) In Comparative Example 4, after the amidation and crosslinking reactions were completed, the thiourea group introduction step was omitted, and the primary amine group relied solely on its monodentate hydrogen bonds with the fluorite surface F. - Function. The single NH bond of the primary amine group with F - The hydrogen bonds formed are of limited strength and have a single interaction mode; however, the two NH bonds in the thiourea group can form bidentate hydrogen bonds with F. - The binding strength is increased by 1-2 orders of magnitude compared to monodentate hydrogen bonds, while the bidentate interaction mode enhances the bonding strength of F. - The spatial location of the collector molecule exhibits greater selectivity. After the thiourea group is removed, the collector molecule shows increased selectivity for the F group on the fluorite surface. - The recognition ability was significantly weakened, leading to a substantial decrease in selectivity. Table 1 shows that the CaF2 grade of the concentrate in Comparative Example 4 was 86.71%, and the recovery rate was 81.44%, both significantly lower than in Example 1. This indicates that the bidentate hydrogen bond recognition of the thiourea group is the core functional unit for the collector to achieve highly selective recognition. Its mechanism of action lies in the synergistic effect of the two hydrogen bonds, precisely capturing the F-active sites on the fluorite surface in a "clamping" configuration, thus achieving highly selective molecular recognition.

[0128] (5) In Comparative Example 5, the amount of thiourea was reduced from 10 parts in Example 1 to 3 parts, resulting in insufficient bidentate hydrogen bond density, which led to the collector molecules affecting the F on the fluorite surface. -The "pincer" trapping ability of the collector was significantly weakened, making it unable to effectively distinguish the microscopic differences in calcium sites on the surfaces of fluorite and calcite. This resulted in a decrease in the inhibitory effect on calcite, with the concentrate grade decreasing by 8.06 percentage points and the recovery rate decreasing by 4.06 percentage points compared to Example 1. This demonstrates that high-calcium ores require a higher thiourea density to enhance bidentate hydrogen bond recognition. In Comparative Example 10, the amount of thiourea was increased from 12 parts in Example 2 to 20 parts. The excessive thiourea groups increased the density of sulfur atoms in the molecule. Since sulfur atoms have certain soft base properties, they can competitively coordinate with iron ions and rare earth ions in iron-containing rare earth tailings, interfering with the selective inhibition of iron minerals by the inhibitor. At the same time, the excessively enhanced hydrogen bond recognition may lead to overly strong adsorption of the collector on the surface of fluorite, which in turn affects the desorption and cleaning efficiency. The concentrate grade decreased by 5.78 percentage points and the recovery rate decreased by 6.04 percentage points compared to Example 2, indicating that there is an optimal range for the thiourea ratio. In Comparative Example 14, the amount of thiourea was increased from 3 parts in Example 3 to 10 parts. For silicate-type fluorite ore (low calcite content, mainly quartz), the excessively high thiourea density caused the collector molecules to focus excessively on F site recognition, neglecting the hydrophobic synergy with the main collector. Simultaneously, the excessively strong recognition ability may cause the collector to form an overly dense adsorption layer on the fluorite surface, hindering the effective coverage of the main collector. The concentrate grade decreased by 5.83 percentage points compared to Example 3, and the recovery rate decreased by 7.77 percentage points. These results verify the scientific principle that the thiourea ratio needs to be precisely controlled according to the calcite content and associated mineral type of the ore: high-calcium ores require a higher thiourea density to enhance selective recognition; iron-rare earth tailings require controlling the upper limit of thiourea to avoid interference from metal ion competition; and silicate-type ores should use a lower thiourea density to balance the synergistic relationship between recognition and collection. This fully reflects the core innovation of the present invention: dynamic control based on ore type.

[0129] (6) Mixture Ratio: The mixture ratio of the collector and the main collector determines the synergistic efficiency of the fluorine site recognition function and the hydrophobic collection function. The collector molecules preferentially recognize the F- active sites on the fluorite surface through the bidentate hydrogen bonds of the primary amine and thiourea groups, forming "marking points" on the mineral surface, which provide precise navigation for the subsequent adsorption of the main collector; the main collector, with its strong hydrophobic properties, forms a dense coating layer around the marked sites, and the two form an ordered mixed adsorption structure on the mineral surface. In Example 1, the mixture ratio was 40:60, and the concentrate CaF2 grade was 98.21% and the recovery rate was 91.27%; while in Comparative Example 6, the mixture ratio was reduced to 20:80, and the proportion of collector was insufficient, which weakened the fluorine site recognition function, failed to effectively mark the active sites on the fluorite surface, and the adsorption of the main collector lacked precise guidance, resulting in a decrease in selectivity, a decrease in concentrate grade to 87.41%, and a decrease in recovery rate to 81.22%. In Example 2, the compound ratio was 25:75, yielding a concentrate CaF2 grade of 96.12% and a recovery rate of 80.27%. However, in Comparative Example 11, the compound ratio was reduced to 10:90, resulting in an excessively low collector ratio. This failed to effectively suppress iron mineral interference in iron-rare earth tailings ores, and the excessive amount of the main collector may have increased mechanical entrainment, leading to a concentrate grade of 87.63% and a recovery rate of 71.28%. In Example 3, the compound ratio was 15:85, yielding a concentrate CaF2 grade of 98.95% and a recovery rate of 95.41%. In Comparative Example 15, the compound ratio was increased to 30:70. For silicate-type fluorite ore, this excessive collector ratio resulted in over-recognition. Excessive fluorine site recognition groups may have limited the adsorption space of the main collector, and over-labeling may have triggered weak adsorption of some gangue minerals, resulting in a concentrate grade of 92.17% and a recovery rate of 90.25%. The above results indicate that the blending ratio needs to be precisely set according to the type of gangue minerals in the ore and the requirement for selective identification, so that the "identification-collection" synergistic mechanism is in the best balance. Too high or too low a ratio will destroy the synergistic efficiency.

[0130] (7) Proportion of non-polar hydrocarbon oil: Non-polar hydrocarbon oil regulates the stability, dispersibility and ore-carrying capacity of foam by forming a molecular-level oil film on the surface of bubbles. Its effect is non-linearly related to the amount added and must be precisely controlled according to the type of ore. In Example 1, the amount of hydrocarbon oil was 12%, and the concentrate CaF2 grade was 98.21% and the recovery rate was 91.27%. However, in Comparative Example 7, the amount of hydrocarbon oil was reduced to 3%, and the foam stability was insufficient. The oil film on the surface of the bubbles was too thin and could not effectively inhibit the excessive rupture of mineralized foam. Slight drop-off occurred in the beneficiation operation, and the recovery rate dropped to 85.64%. In Example 2, the amount of hydrocarbon oil was 6%, and the concentrate CaF2 grade was 96.12% and the recovery rate was 80.27%. However, in Comparative Example 12, the amount of hydrocarbon oil was reduced to 3%, and the foam stability was also insufficient. Especially in iron-containing rare earth tailings type ores, iron minerals easily make the foam sticky. When the amount of hydrocarbon oil is insufficient, the foam is fragile, and the recovery rate drops to 76.68%. In Example 3, the hydrocarbon oil dosage was 2%, resulting in a CaF2 concentrate grade of 98.95% and a recovery rate of 95.41%. In Comparative Example 16, the hydrocarbon oil dosage was increased to 8%, leading to excessively dense foam and a thick oil film on the bubble surface. This resulted in overly stable foam that was difficult to break, causing an excessively thick foam layer during skimming and reduced ore carrying capacity. Furthermore, excessive defoaming could cause some mineralized particles to detach, reducing the recovery rate to 88.62%. These results indicate that the effect of hydrocarbon oil dosage on foam stability is non-linear. For silicate ores, excessively sticky foam requires moderate defoaming; for carbonate ores, foam stabilization is necessary in beneficiation operations; and for iron- and rare-earth tailings, foam performance needs to be balanced. Fine-tuning based on the ore type is essential to achieve the optimal balance between foam performance and flotation efficiency.

[0131] (8) Low-temperature adaptability: Due to the rigid molecular structure, the adsorption process of traditional fatty acid collectors depends on temperature to overcome the activation energy barrier. Under low-temperature conditions, the molecular chain movement is hindered, the dispersibility is poor, and it is difficult to form an effective coating on the mineral surface, resulting in a sharp decrease in recovery rate. Example 1 obtained a concentrate CaF2 grade of 98.21% and a recovery rate of 91.27% at room temperature; while Comparative Example 8 used traditional sodium oleate for flotation at room temperature, and the concentrate grade was only 94.25% and the recovery rate was only 56.37%, which were 3.96 and 34.90 percentage points lower than those of Example 1, respectively; after heating the traditional sodium oleate to 30°C in Comparative Example 9, the molecular thermal motion was enhanced, the dispersibility was improved, and the recovery rate was increased to 86.61%, but the concentrate grade was still lower than that of Example 1. Example 2 yielded a CaF2 concentrate with a grade of 96.12% and a recovery rate of 80.27% at room temperature. In contrast, Comparative Example 13, using conventional oleic acid flotation at room temperature, achieved a concentrate grade of 87.86% and a recovery rate of only 50.37%, representing decreases of 8.26 and 29.90 percentage points respectively compared to Example 2. This indicates that traditional reagents have poorer selectivity in iron-rare earth tailings type ores. Example 3 yielded a CaF2 concentrate with a grade of 98.95% and a recovery rate of 95.41% at room temperature. In contrast, Comparative Example 17, using conventional tall oil flotation at room temperature, achieved a concentrate grade of 96.67% and a recovery rate of only 82.11%, representing decreases of 2.28 and 13.30 percentage points respectively compared to Example 3. The primary amine and thiourea groups introduced into the collector molecule of this invention react with the F2 groups on the fluorite surface. - The hydrogen bonding effect does not depend on temperature to overcome the activation energy barrier. Ethylene glycol gives it good low-temperature fluidity, which can be quickly dissolved and dispersed at room temperature to achieve efficient adsorption. This breaks through the technical bottleneck of traditional collectors that rely on heating the slurry and significantly reduces flotation energy consumption.

[0132] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A process for the preparation of a mineralogically based fluorite flotation collector, characterized by: It consists of the following steps: (1) Amide reaction: Mix vegetable oil with ethylene glycol, heat to 60-80℃, add ethylenediamine, then raise the temperature to 140-160℃ and keep it at that temperature for 3-5 hours. Remove the generated water through a reflux condenser to obtain fatty acyl ethylenediamine intermediate; (2) Crosslinking reaction: The fatty acyl ethylenediamine intermediate prepared in step (1) is cooled to 80-100℃, and then terephthalic acid is added and reacted for 1-2 hours to obtain the crosslinked modified intermediate; (3) Thiourea group introduction: Thiourea is added to the crosslinking modified intermediate prepared in step (2) to modify the functional groups and prepare fluorite flotation collector; Wherein: the amount of thiourea added in step (3) is adjusted according to the type of gangue mineral in the fluorite ore: ① when the gangue mineral is silicate, the mass ratio of thiourea to vegetable oil is 2-5:100; ② when the gangue mineral is carbonate, the mass ratio of thiourea to vegetable oil is 5-20:100; ③ when the gangue mineral is rare earth and magnetic iron, the mass ratio of thiourea to vegetable oil is 10-15:

100.

2. The process for the preparation of mineral based genetically identified fluorite flotation collector as claimed in claim 1 wherein: The vegetable oil mentioned in step (1) is one of oleic acid, soybean oil, rapeseed oil and their acidified oils; In step (1), the mass of ethylene glycol accounts for 40%-80% of the mass of the vegetable oil; In step (1), the mass ratio of vegetable oil to ethylenediamine is 100: 20-40.

3. The process for the preparation of mineral based specific fluorite flotation collector as claimed in claim 1 wherein: In step (2), the mass ratio of terephthalic acid to vegetable oil in step (1) is 10-25:

100.

4. The preparation method of the fluorite flotation collector based on mineral gene recognition according to claim 1, characterized in that: In step (3), the reaction temperature is 80-95℃ and the reaction time is 1-2h.

5. The application of the fluorite flotation collector based on mineral gene recognition as described in claim 1, characterized in that: The flotation reagent system is adjusted according to the genetic characteristics of fluorite ore, and consists of the following steps: fluorite ore is ground to -0.074 mm (50%-95%), pH adjuster is added to adjust the pH of the pulp to 8-10, gangue inhibitor, a mixture of fluorite flotation collector and main collector based on mineral gene recognition, and non-polar hydrocarbon oil are added sequentially, and after one roughing, multiple cleaning and scavenging, fluorite concentrate and tailings are obtained.

6. The application of the fluorite flotation collector based on mineral gene recognition according to claim 5, characterized in that: The mass ratio of the fluorite flotation collector based on mineral gene recognition to the main collector in the compound mixture is determined according to the type of gangue minerals in the fluorite ore: ① When the gangue minerals are silicates, the mass ratio of the fluorite flotation collector based on mineral gene recognition to the main collector is 10:90 ~ 20:80; ② When the gangue minerals are carbonates, the mass ratio of the fluorite flotation collector based on mineral gene recognition to the main collector is 30:70 ~ 40:60; ③ When the gangue minerals are rare earth elements and magnetic iron, the mass ratio of the fluorite flotation collector based on mineral gene recognition to the main collector is 20:80 ~ 30:

70.

7. The application of the fluorite flotation collector based on mineral gene recognition according to claim 5, characterized in that: The non-polar hydrocarbon oil is kerosene or diesel oil. The amount of non-polar hydrocarbon oil added is determined according to the type of gangue mineral in the fluorite ore: ① When the gangue mineral is silicate, the mass of the non-polar hydrocarbon oil is 0-5% of the mass of the compound mixture; ② When the gangue mineral is carbonate, the mass of the non-polar hydrocarbon oil is 5-12% of the mass of the compound mixture; ③ When the gangue mineral is rare earth and magnetic iron, the mass of the non-polar hydrocarbon oil is 5-8% of the mass of the compound mixture.

8. The application of the fluorite flotation collector based on mineral gene recognition according to claim 5, characterized in that: The mass concentration of the flotation pulp is 25%~40%, and the pH adjuster is sodium carbonate; the gangue inhibitor is one or more of water glass, carboxymethyl cellulose, tannin, or acidified water glass, with a dosage of 500-2000 g / t; the main collector is one or more of sodium oleate, oleic acid, or tall oil, with a dosage of 200-1000 g / t; in the scavenging operation, a compound mixture of fluorite flotation collector and main collector based on mineral gene recognition and non-polar hydrocarbon oil are added. The dosage of the compound mixture of fluorite flotation collector and main collector based on mineral gene recognition is 1 / 4 to 1 / 2 of that in the previous operation, and the dosage of non-polar hydrocarbon oil is 1 / 4 to 1 / 2 of that in the previous operation; in the cleaning operation, gangue inhibitor is added, with a dosage of 1 / 4 to 1 / 2 of that in the previous operation.

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