Rare earth mineral collecting agent containing polybasic heterocyclic structure and preparation method thereof

Abstract

The application relates to a rare earth mineral collecting agent containing a multi-element heterocyclic structure and a preparation method thereof. In the first step, furan (or cyclopentadiene, pyrrole, thiophene, etc.) and maleic anhydride are used as raw materials, the molar ratio is 1:1.0-1.2, dichloromethane is used as a solvent, and a multi-element heterocyclic anhydride is generated by reacting at 20 DEG C-60 DEG C; in the second step, the multi-element heterocyclic anhydride, hydroxylamine hydrochloride and an inorganic salt are used as raw materials, the molar ratio is 1:1.1-1.5:2.2-2.6, water is used as a solvent, the inorganic salt is used as a neutralizing agent, and the collecting agent is obtained by reacting at 50 DEG C-80 DEG C for 3.5 hours, vacuum filtering and drying.

Description

TECHNICAL FIELD

[0001] The present application relates to a rare earth mineral collector containing a multi-heterocyclic structure and a preparation method thereof, and belongs to the technical field of mineral processing reagents. BACKGROUND

[0002] Rare earth is an important strategic resource, and is known as "modern industrial vitamin" and "21st century new material treasure". However, the flotation separation of rare earth ore is difficult, so improving the flotation separation index of rare earth ore has been the direction of efforts of relevant scientific and technological workers. As a high-efficiency collector for rare earth ore flotation, hydroxamic acid has better collecting ability and selectivity than the conventional fatty acid collector, and has been widely used in industry. This is mainly because the oxime group in the molecular structure of hydroxamic acid contains oxygen and nitrogen atoms, both of which have lone pair electrons, and can chelate with metal ions Fe 3+ , Ti 4+ , Cu 2+ , etc. to form stable chelates. Most of the rare earth flotation reagents used in industry are hydroxamic acid complex reagents, and there is a certain difference in selectivity and collecting ability. In the present application, a new type of rare earth mineral collector containing a multi-heterocyclic structure, a double chelating group and an amide group is synthesized. The introduction of a multi-heterocyclic structure and an amide group in the molecular structure of the collector enhances its solubility and dispersion ability in the ore pulp. At the same time, the N-hydroxyl group and the adjacent carbon-oxygen double bond form a double chelating group, which enhances the combination with rare earth metal ions, and can effectively improve the collecting ability and beneficiation efficiency of the collector. SUMMARY

[0003] The purpose of the present application is to synthesize a new type of rare earth mineral collector with a novel structure, stable performance, good collecting ability and selectivity.

[0004] The present application provides a rare earth mineral collector containing a multi-heterocyclic structure, and the structure of the collector is as follows:

[0005]

[0006] wherein R is H, aryl or alkyl; X is CH2, O, S or NH.

[0007] The present application provides a preparation method of a rare earth mineral collector containing a multi-heterocyclic structure, and the method comprises the following steps:

[0008] (1) Synthesis of multi-heterocyclic anhydride: using furan (or cyclopentadiene, pyrrole, thiophene, etc.) and maleic anhydride as raw materials, dichloromethane as solvent, and reacting at 20-60℃ to generate multi-heterocyclic anhydride.

[0009] (2) Synthesis of polyheterocyclic imide: polyheterocyclic anhydride and hydroxylamine hydrochloride are used as raw materials, water is used as solvent, inorganic salt is used as neutralizing agent, reaction is carried out at 50-80℃ for 3.5 hours, vacuum filtration and drying are carried out to obtain the collector.

[0010] In the technical solution, further, in step (1), the solvent dichloromethane and maleic anhydride are added first, stirring and dispersing for 30 minutes, then furan (or cyclopentadiene, pyrrole, thiophene, etc.) is added dropwise into the reaction system.

[0011] In the technical solution, further, in step (1), the molar ratio of furan (or cyclopentadiene, pyrrole, thiophene, etc.) and maleic anhydride is 1:1.0-1.2, and the reaction is carried out for 3-5 hours.

[0012] In the technical solution, further, in step (2), n (polyheterocyclic anhydride) : n (hydroxylamine hydrochloride) : n (inorganic salt) = 1:1.1-1.5:2.2-2.6.

[0013] In the technical solution, further, in step (2), the inorganic salt is preferably sodium hydroxide or sodium carbonate. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 It is a process for preparing a rare earth mineral collector containing a polyheterocyclic structure. DETAILED DESCRIPTION

[0015] The rare earth mineral collector containing a polyheterocyclic structure provided by the application mainly comprises a polyheterocyclic imide compound, and contains a polyheterocyclic structure, a double chelating group and an imide polar group.

[0016] The preparation method of the rare earth mineral collector containing a polyheterocyclic structure provided by the application is as follows: furan (or cyclopentadiene, pyrrole, thiophene, etc.) and maleic anhydride are reacted in a dichloromethane solvent to generate polyheterocyclic anhydride, then the polyheterocyclic anhydride is reacted with hydroxylamine hydrochloride under the condition of neutralization by an inorganic salt to generate N-hydroxyl polyheterocyclic imide, vacuum filtration and drying are carried out to obtain the collector.

[0017] The synthesis method adopted by the application comprises the following steps:

[0018] (1) Synthesis of polyheterocyclic anhydride: furan (or cyclopentadiene, pyrrole, thiophene, etc.) and maleic anhydride are used as raw materials, dichloromethane is used as solvent, and reaction is carried out at 20-60℃ to generate polyheterocyclic anhydride.

[0019] (2) Synthesis of polyheterocyclic imide: polyheterocyclic anhydride and hydroxylamine hydrochloride are used as raw materials, water is used as solvent, inorganic salt is used as neutralizing agent, reaction is carried out at 50-80℃ for 3.5 hours, vacuum filtration and drying are carried out to obtain the collector.

[0020] The new rare earth ore collector of the present application has a mass percentage of 2% in the water solution of the rare earth ore collector when the product performance is determined. The flotation process is consistent with the field process.

[0021] Example 1

[0022] A certain amount of maleic anhydride and solvent dichloromethane are taken in a flask, stirred for 30 minutes, and then 0.8 times the molar amount of furan is added dropwise, heated to 40℃, and reacted for 4 hours. The reaction system is cooled to room temperature, and the generated solid is filtered out under reduced pressure. A certain amount of the solid and solvent water are taken in a flask, 1.1 times the molar amount of hydroxylamine hydrochloride is added, and stirred and dispersed for 20 minutes. 2.3 times the molar amount of sodium hydroxide is prepared into a 30% mass fraction aqueous solution, added dropwise to the reaction system, heated to 70℃, and reacted for 3.5 hours. The reaction system is cooled to room temperature, filtered under vacuum, and dried to obtain a rare earth ore collector containing a multi-heterocyclic structure.

[0023] The new structure reagent is used to perform experiments on the iron tailings from a certain place in Inner Mongolia. The raw ore contains 9.56% of rare earth REO, fluorite, feldspar, mica, calcite, and other components, and is difficult to separate.

[0024] The experiments are performed under the premise of the original process flow, grinding fineness, and pulp concentration, and the new structure reagent is evaluated by using a one-roughing-two-cleaning production process. The results are as follows:

[0025] Raw ore rare earth content % Concentrate rare earth content % Tailing rare earth content % Recovery % New collector 9.64 56.43 3.94 63.57

[0026] The test results show that the new structure reagent has good collecting capacity for the rare earth ore in the ore.

[0027] Example 2

[0028] A certain amount of maleic anhydride and solvent dichloromethane are taken in a flask, 0.9 times the molar amount of pyrrole is added dropwise, heated to 50℃, and reacted for 3.5 hours. The reaction system is cooled to room temperature, and the generated solid is filtered out under reduced pressure. A certain amount of the solid and solvent water are taken in a flask, 1.2 times the molar amount of hydroxylamine hydrochloride is added, and stirred and dispersed for 20 minutes. 2.5 times the molar amount of sodium hydroxide is prepared into a 30% mass fraction aqueous solution, added dropwise to the reaction system, heated to 80℃, and reacted for 3.5 hours. The reaction system is cooled to room temperature, filtered under vacuum, and dried to obtain a rare earth ore collector containing a multi-heterocyclic structure.

[0029] The new structure reagent is used to perform experiments on the strong magnetic medium ore from a certain place in Inner Mongolia. The raw ore contains 7.31% of rare earth REO, fluorite, mica, and apatite, and other components, and is difficult to separate.

[0030] The experiment was carried out under the premise of the original process flow, grinding fineness and pulp concentration, and the new structure reagent was evaluated by using one roughing and two cleaning process, and the results were as follows:

[0031] Raw ore rare earth content % Concentrate rare earth content % Tailing rare earth content % Recovery % New collector 7.44 56.22 3.01 62.91

[0032] The test results show that for the ore, the new structure reagent has good collecting ability for the rare earth minerals.

[0033] Example 3

[0034] A certain amount of maleic anhydride and solvent dichloromethane were taken in a flask, stirred for 30 minutes, and then an equimolar amount of thiophene was added dropwise. The reaction was heated to 60°C for 5 hours, cooled to room temperature, and the generated solid was filtered out under reduced pressure. A certain amount of solid and solvent water were taken in a flask, 1.3 times the molar amount of hydroxylamine hydrochloride was added, and stirred and dispersed for 20 minutes. 2.6 times the molar amount of sodium hydroxide was prepared into a 30% mass fraction aqueous solution, added dropwise to the reaction system, heated to 75°C, and reacted for 3.5 hours. After cooling to room temperature, vacuum filtration and drying were carried out to obtain a rare earth mineral collector containing a multi-heterocyclic structure.

[0035] The new reagent was used to experiment on a rare earth ore from a certain place in Sichuan, which contains 3.31% of rare earth REO in the raw ore, as well as barite, mica and apatite, etc., with complex composition and difficult separation.

[0036] The experiment was carried out under the premise of the original process flow, grinding fineness and pulp concentration, and the new structure reagent was evaluated by using one roughing and two cleaning process, and the results were as follows:

[0037] Raw ore rare earth content % Concentrate rare earth content % Tailing rare earth content % Recovery % New collector 3.21 27.46 0.96 72.63

[0038] The test results show that for the ore, the new structure reagent has good collecting ability for the rare earth minerals.

[0039] Example 4

[0040] A certain amount of maleic anhydride and solvent dichloromethane were taken in a flask, stirred for 30 minutes, and then an equimolar amount of thiophene was added dropwise. The reaction was heated to 60°C for 5 hours, cooled to room temperature, and the generated solid was filtered out under reduced pressure. A certain amount of solid and solvent water were taken in a flask, 1.3 times the molar amount of hydroxylamine hydrochloride was added, and stirred and dispersed for 20 minutes. 2.6 times the molar amount of sodium hydroxide was prepared into a 30% mass fraction aqueous solution, added dropwise to the reaction system, heated to 75°C, and reacted for 3.5 hours. After cooling to room temperature, vacuum filtration and drying were carried out to obtain a rare earth mineral collector containing a multi-heterocyclic structure.

[0041] The new reagent was used in the experiment of a rare earth ore from Yunnan, which contains REO 5.31%, dolomite, mica, quartz, apatite and other components, and is difficult to separate.

[0042] The experiment was carried out under the premise of the original process, grinding fineness and pulp concentration, and the new reagent was evaluated by adopting one roughing and three cleaning process, and the results are as follows:

[0043] Raw ore rare earth content % Concentrate rare earth content % Tailing rare earth content % Recovery % New collector Raw ore rare earth content % Concentrate rare earth content % Tailing rare earth content % Recovery % New collector 5.33 29.46 1.46 76.39

[0044] The test results show that the new reagent has good collecting ability for rare earth minerals in the complex ore from Yunnan.

Claims

1. A rare earth mineral collector containing a polycyclic heterocyclic structure, characterized in that: The collector has the following general structural formula: wherein R is H, aryl or alkyl, and X is CH2, O, S or NH.

2. A method for preparing a rare earth mineral collector containing a polycyclic heterocyclic structure, characterized in that Use the following steps: (1) Synthesis of polycyclic heterocyclic anhydrides: Furan, cyclopentadiene, pyrrole or thiophene and maleic anhydride are used as raw materials, dichloromethane is used as solvent, and the reaction is carried out at 20°C-60°C to generate polycyclic heterocyclic anhydrides; (2) Synthesis of polycyclic heterocyclic imide: polycyclic heterocyclic anhydride and hydroxylamine hydrochloride are used as raw materials, water is used as solvent, and inorganic salt is used as neutralizing agent. The reaction is carried out at 50℃-80℃ for 3.5 hours, and the collector is obtained by vacuum filtration and drying.

3. The method for preparing a rare earth mineral collector containing a polycyclic heterocyclic structure according to claim 2, characterized in that In step (1), solvents such as dichloromethane and maleic anhydride are first added, stirred and dispersed for 30 minutes, and then any one of furan, cyclopentadiene, pyrrole or thiophene is added dropwise to the reaction system.

4. The method for preparing a rare earth mineral collector containing a polycyclic heterocyclic structure according to claim 2, characterized in that In step (1), the molar ratio of furan, cyclopentadiene, pyrrole or thiophene to maleic anhydride is 1:1.0-1.2, and the reaction is carried out for 3-5 hours.

5. The method for preparing a rare earth mineral collector containing a polycyclic heterocyclic structure according to claim 2, characterized in that In step (2), the molar ratio of the polycyclic heterocyclic anhydride, hydroxylamine hydrochloride and inorganic salt is 1:1.1-1.5:2.2-2.

6.

6. The method for preparing a rare earth mineral collector containing a polycyclic heterocyclic structure according to claim 2, characterized in that The inorganic salt in step (2) is sodium carbonate.

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