Rare earth ore composite collector and its preparation method and application

Abstract

The present invention discloses a rare earth ore composite collector and a preparation method and application thereof, and belongs to the technical field of rare earth ore collectors. The rare earth ore composite collector comprises 2-hydroxy-3-naphthohydroxamic acid and 3-hydroxy-2-naphthoyl hydrazide. The present invention also proposes a preparation method of the rare earth ore composite collector, and the 2-hydroxy-3-naphthohydroxamic acid and the 3-hydroxy-2-naphthoyl hydrazide are mixed to obtain the rare earth ore composite collector. The present invention also proposes an application of the rare earth ore composite collector or the rare earth ore composite collector obtained by the above-mentioned preparation method in the flotation of fluorocarbon cerium ore, and the rare earth ore composite collector and an inhibitor are added to the rough ore dressing of fluorocarbon cerium ore for flotation. The composite collector proposed in the present application has high ore dressing efficiency; the unit consumption of reagents is low, and the flotation cost is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of rare earth ore collectors, and in particular to a rare earth ore composite collector and a preparation method and application thereof. Background Art

[0002] Rare earth mineral processing technology is mainly based on flotation, supplemented by gravity separation and magnetic separation. According to the properties of the ore, the rare earth mineral processing technology in different mining areas is different.

[0003] At present, the commonly used mineral processing agents for the flotation of fluorocarbon cerium rare earth ores include the following four types, namely: ① hydroxamic acid; ② phosphorus-containing; ③ sulfur-containing; ④ carboxylic acid. Hydroxamic acid is a highly selective mineral processing agent that can be used for the flotation of a variety of oxide ores. At present, the main problems of hydroxamic acid in the field of mineral flotation are high reagent cost and large usage. At the same time, due to the unevenness of the mineral surface and the performance differences between different reagents, a single hydroxamic acid is difficult to achieve a good separation effect due to the complex and changeable properties of the ore, which to a certain extent limits the development and utilization of rare earth ores. Therefore, it is urgent to develop a new type of composite mineral processing agent to solve the above-mentioned process pain points. Summary of the invention

[0004] The purpose of the present invention is to overcome the above technical deficiencies, provide a rare earth ore composite collector and its preparation method and application, and solve the technical problems of high cost and large amount of reagents used in mineral flotation in the prior art.

[0005] In order to achieve the above technical purpose, the technical solution of the present invention provides a rare earth mineral composite collector, including 2-hydroxy-3-naphthohydroxamic acid and 3-hydroxy-2-naphthoylhydrazide.

[0006] In some embodiments, the mass ratio of the 2-hydroxy-3-naphthohydroxamic acid to the 3-hydroxy-2-naphthoylhydrazide is (3-9):1.

[0007] In some embodiments, the mass ratio of the 2-hydroxy-3-naphthohydroxamic acid to the 3-hydroxy-2-naphthoylhydrazide is (4-5):1.

[0008] In some embodiments, the 2-hydroxy-3-naphthohydroxamic acid is prepared by the following steps: 3-hydroxy-2-naphthoic acid methyl ester and hydrazine hydrate are mixed in a molar ratio of (0.8-2):1, and then reacted at a temperature of 60-90°C.

[0009] In some embodiments, the 3-hydroxy-2-naphthoic acid methyl ester and the hydrazine hydrate are mixed and then reacted at a temperature of 80-85° C. to obtain the obtained product.

[0010] In some embodiments, the 3-hydroxy-2-naphthoic acid hydrazide is prepared by the following steps: 3-hydroxy-2-naphthoic acid methyl ester, hydroxylamine hydrochloride and NaOH solution are mixed, and then reacted at a temperature of 0-50°C.

[0011] In some embodiments, the 3-hydroxy-2-naphthoic acid methyl ester, the hydroxylamine hydrochloride and the NaOH solution are mixed and then reacted at a temperature of 25-30° C. to obtain.

[0012] In addition, the present invention also provides a method for preparing the rare earth mineral composite collector, wherein the 2-hydroxy-3-naphthohydroxamic acid and the 3-hydroxy-2-naphthoylhydrazide are mixed to obtain the rare earth mineral composite collector.

[0013] In addition, the present invention also proposes an application of the rare earth ore composite collector or the rare earth ore composite collector prepared by the above preparation method in bastnaesite flotation, and the rare earth ore composite collector and an inhibitor are added to the bastnaesite roughing to carry out flotation.

[0014] In some embodiments, the amount of rare earth ore composite collector added to each ton of bastnaesite for flotation is 32-34 kg; and / or, the inhibitor is one or more of water glass, alum, sodium fluorosilicate, carboxymethyl cellulose and citric acid.

[0015] Compared with the prior art, the beneficial effects of the present invention include: when the composite collector proposed in the present application is used, due to the unevenness of the mineral surface and the performance differences between different reagents, it is difficult for a single hydroxamic acid to achieve a good separation effect due to the complex and changeable properties of the ore; when a mixed agent is used, the two compounds in the composite collector can respectively undergo a chelation reaction with the rare earth ore to generate two five-membered ring chelates of -C=O-RE-ON- and -C=O-RE-NN-, which can complement each other, and at the same time, the naphthalene ring in the composite molecule strengthens the hydrophobicity, thereby achieving the effect of improving the flotation efficiency, and the ore dressing efficiency is high; the unit consumption of the reagent is low, and the flotation cost is reduced. The present invention overcomes the disadvantage of low ore dressing efficiency when a single collector is used in the traditional method, and reduces the ore dressing cost while improving the ore dressing efficiency; the preparation process is simple, the operation is simple, safe and controllable, and it is easy to industrialize production. DETAILED DESCRIPTION

[0016] This specific embodiment provides a rare earth mineral composite collector, including 2-hydroxy-3-naphthohydroxamic acid and 3-hydroxy-2-naphthoylhydrazide. When the mixed drug is used, it can complement each other, and its function is equivalent to a new type of reagent, thereby improving the flotation index and reducing the reagent content.

[0017] In any embodiment, the mass ratio of the 2-hydroxy-3-naphthohydroxamic acid to the 3-hydroxy-2-naphthoylhydrazide is (3-9): 1. The collector according to this ratio can float bastnaesite well.

[0018] In some embodiments, the mass ratio of the 2-hydroxy-3-naphthohydroxamic acid to the 3-hydroxy-2-naphthoylhydrazide is (4-5): 1. The collector according to this ratio can better float bastnaesite.

[0019] In any embodiment, the 2-hydroxy-3-naphthohydroxamic acid is prepared by the following steps: 3-hydroxy-2-naphthoic acid methyl ester and hydrazine hydrate are mixed in a molar ratio of (0.8-2):1, and then reacted at a temperature of 60-90°C. More preferably, the 3-hydroxy-2-naphthoic acid methyl ester and the hydrazine hydrate are mixed, and then reacted at a temperature of 80-85°C.

[0020] In any embodiment, the 3-hydroxy-2-naphthoic acid hydrazide is prepared by the following steps: 3-hydroxy-2-naphthoic acid methyl ester, hydroxylamine hydrochloride and NaOH solution are mixed, and then reacted at a temperature of 0-50°C; more preferably, the 3-hydroxy-2-naphthoic acid methyl ester, hydroxylamine hydrochloride and NaOH solution are mixed, and then reacted at a temperature of 25-30°C.

[0021] The reaction equation of 2-hydroxy-3-naphthohydroxamic acid and 3-hydroxy-2-naphthoylhydrazide is as follows:

[0022]

[0023] This specific embodiment also proposes a method for preparing the above-mentioned rare earth ore composite collector, mixing the 2-hydroxy-3-naphthohydroxamic acid and the 3-hydroxy-2-naphthoylhydrazide to obtain the rare earth ore composite collector, and adding the rare earth ore composite collector and an inhibitor to the fluorocarbon cerium roughing ore for flotation.

[0024] This specific embodiment also proposes an application of the above-mentioned rare earth ore composite collector or the rare earth ore composite collector prepared by the above-mentioned preparation method in the flotation of fluorocarbon cerium ore, and the amount of the rare earth ore composite collector added per ton of fluorocarbon cerium ore for flotation is 32-34 kg; and / or, the inhibitor is one or more of water glass, alum, sodium fluorosilicate, carboxymethyl cellulose and citric acid.

[0025] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0026] In the present invention, reference is made to “some embodiments”, “this embodiment”, examples, etc., which describe a subset of all possible embodiments, but it can be understood that “some embodiments” may be the same subset or different subsets of all possible embodiments and may be combined with each other without conflict.

[0027] If similar descriptions of "first / second" appear in the application documents, the following instructions are added. In the following description, the terms "first\second\third" are merely used to distinguish similar objects and do not represent a specific ordering of the objects. It can be understood that "first\second\third" can be interchanged in a specific order or sequence where permitted, so that the embodiments described herein can be implemented in an order other than that described herein.

[0028] In this embodiment, the term "and / or" is merely a description of the association relationship between associated objects, indicating that three relationships may exist. For example, object A and / or object B may represent three situations: object A exists alone, object A and object B exist at the same time, and object B exists alone.

[0029] It should be noted that in the following examples or comparative examples, bastnaesite roughing of mixed rare earth ore in Bayan Obo, Inner Mongolia is used as raw material, wherein the REO content is 9.50wt%. The inhibitor in the following examples is water glass. In addition to water glass, in the rare earth ore dressing process, the inhibitor can also be alum, sodium fluorosilicate, carboxymethyl cellulose or citric acid.

[0030] Example 1

[0031] This embodiment provides a composite collector, which is prepared by the following steps:

[0032] Dissolve 40.0 g (0.1978 mol) of methyl 3-hydroxy-2-naphthoate in 50 g of anhydrous ethanol, then add 32 g (0.2557 mol) of hydrazine hydrate, heat to 80°C and reflux and continue to react for 6-8 h. After the reaction of the raw materials is complete, filter and dry in a vacuum oven at 40°C for 8 h to obtain 3-hydroxy-2-naphthoic acid hydrazide (39 g) with a yield of 97.5%.

[0033] Dissolve 16.8 g NaOH (0.4195 mol) in 100 g water to prepare NaOH solution; dissolve 26.5 g (0.1311 mol) 3-hydroxy-2-naphthoic acid methyl ester in NaOH solution, add 10.9 g (0.1573 mol) hydroxylamine hydrochloride, stir at room temperature 25°C for 4 h to obtain an aqueous solution of 2-hydroxy-3-naphthohydroxamic acid (theoretical yield 26.6 g). Then add 6.7 g 3-hydroxy-2-naphthoic acid hydrazide solid, continue stirring at room temperature for 0.5 h, and obtain a composite collector aqueous solution (the mass ratio of 2-hydroxy-3-naphthohydroxamic acid to 3-hydroxy-2-naphthoic acid hydrazide is 4:1).

[0034] This embodiment also proposes the application of the composite collector in this embodiment, which is as follows:

[0035] The raw material is the bastnaesite roughing of the mixed rare earth mine in Bayan Obo, Inner Mongolia, with a REO content of 9.50wt%.

[0036] The collector aqueous solution prepared in this example was added to the fluorocarbon cerium ore roughing at an addition amount of 32.0 kg of the composite collector per ton of the fluorocarbon cerium ore roughing, and an inhibitor was added at an addition amount of 1 kg of water glass per ton of the fluorocarbon cerium ore roughing, and flotation was carried out for 5 minutes to obtain a flotation concentrate (grade 65%) and a flotation tailings (grade 6%).

[0037] Example 2

[0038] This embodiment proposes the application of the composite collector prepared in Example 1, which is as follows:

[0039] The collector aqueous solution prepared in Example 1 was added to the fluorocarbon cerium ore roughing, containing 35.0 kg / t of the composite collector, and an inhibitor was added in an amount of 1 kg of water glass per ton of fluorocarbon cerium ore roughing. Flotation was carried out for 5 minutes to obtain a flotation concentrate (grade 63%) and a flotation tailing (grade 6%).

[0040] Example 3

[0041] This embodiment proposes the application of the composite collector prepared in Example 1, which is as follows:

[0042] The collector aqueous solution prepared in Example 1 was added to the bastnaesite roughing, containing 30.0 kg / t of the composite collector, and an inhibitor was added in an amount of 1 kg of water glass per ton of bastnaesite roughing. Flotation was carried out for 5 minutes to obtain a flotation concentrate (grade 62%) and a flotation tailing (grade 6.8%).

[0043] Example 4

[0044] The aqueous solution of 3-hydroxy-2-naphthoyl hydrazide and 2-hydroxy-3-naphthohydroxamic acid in this embodiment is prepared by the method of Example 1; the composite collector proposed in this embodiment is prepared by the following steps:

[0045] To the obtained aqueous solution of 2-hydroxy-3-naphthohydroxamic acid (theoretical yield: 26.6 g) was added 3-hydroxy-2-naphthoylhydrazide (8.9 g) as a solid to obtain a composite collector aqueous solution having a mass ratio of 3:1 between the two.

[0046] This example also proposes the application of the composite collector in this example, and the specific steps are the same as those in Example 1, to obtain flotation concentrate (grade 61.5%) and flotation tailings (grade 6.6%).

[0047] Example 5

[0048] The aqueous solution of 3-hydroxy-2-naphthoyl hydrazide and 2-hydroxy-3-naphthohydroxamic acid in this embodiment is prepared by the method of Example 1; the composite collector proposed in this embodiment is prepared by the following steps:

[0049] To the obtained aqueous solution of 2-hydroxy-3-naphthohydroxamic acid (theoretical yield: 26.6 g) was added 3-hydroxy-2-naphthoylhydrazide (5.3 g) solid to obtain a composite collector aqueous solution with a mass ratio of 5:1 between the two.

[0050] This example also proposes the application of the composite collector in this example, and the specific steps are the same as those in Example 1 to obtain flotation concentrate (grade 65%) and flotation tailings (grade 6.5%).

[0051] Example 6

[0052] The aqueous solution of 3-hydroxy-2-naphthoyl hydrazide and 2-hydroxy-3-naphthohydroxamic acid in this embodiment is prepared by the method of Example 1; the composite collector proposed in this embodiment is prepared by the following steps:

[0053] To the obtained aqueous solution of 2-hydroxy-3-naphthohydroxamic acid (theoretical yield: 26.6 g) was added 3-hydroxy-2-naphthoylhydrazide (4.4 g) as a solid to obtain a composite collector aqueous solution having a mass ratio of 6:1 between the two.

[0054] This example also proposes the application of the composite collector in this example, and the specific steps are the same as those in Example 1, to obtain flotation concentrate (grade 64.5%) and flotation tailings (grade 6.8%).

[0055] Example 7

[0056] The aqueous solution of 3-hydroxy-2-naphthoyl hydrazide and 2-hydroxy-3-naphthohydroxamic acid in this embodiment is prepared by the method of Example 1; the composite collector proposed in this embodiment is prepared by the following steps:

[0057] To the obtained aqueous solution of 2-hydroxy-3-naphthohydroxamic acid (theoretical yield: 26.6 g) was added 3-hydroxy-2-naphthoylhydrazide (3.8 g) as a solid to obtain a composite collector aqueous solution having a mass ratio of 7:1 between the two.

[0058] This example also proposes the application of the composite collector in this example, and the specific steps are the same as those in Example 1, to obtain flotation concentrate (grade 63.8%) and flotation tailings (grade 7.3%).

[0059] Example 8

[0060] The aqueous solution of 3-hydroxy-2-naphthoyl hydrazide and 2-hydroxy-3-naphthohydroxamic acid in this embodiment is prepared by the method of Example 1; the composite collector proposed in this embodiment is prepared by the following steps:

[0061] To the obtained aqueous solution of 2-hydroxy-3-naphthohydroxamic acid (theoretical yield: 26.6 g) was added 3-hydroxy-2-naphthoylhydrazide (3.3 g) solid to obtain a composite collector aqueous solution with a mass ratio of 8:1 between the two.

[0062] This example also proposes the application of the composite collector in this example, and the specific steps are the same as those in Example 1, to obtain flotation concentrate (grade 62.5%) and flotation tailings (grade 7.9%).

[0063] Example 9

[0064] The aqueous solution of 3-hydroxy-2-naphthoyl hydrazide and 2-hydroxy-3-naphthohydroxamic acid in this embodiment is prepared by the method of Example 1; the composite collector proposed in this embodiment is prepared by the following steps:

[0065] To the obtained aqueous solution of 2-hydroxy-3-naphthohydroxamic acid (theoretical yield: 26.6 g) was added 3-hydroxy-2-naphthoylhydrazide (3.0 g) solid to obtain a composite collector aqueous solution with a mass ratio of 9:1 between the two.

[0066] This example also proposes the application of the composite collector in this example, and the specific steps are the same as those in Example 1, to obtain flotation concentrate (grade 62%) and flotation tailings (grade 8%).

[0067] Comparative Example 1

[0068] The only difference between this comparative example and Example 1 is that no water glass inhibitor is added in the application of the composite collector, and only 2-hydroxy-3-naphthohydroxamic acid and 3-hydroxy-2-naphthoyl hydrazide in the amount of Example 1 are added, and an equal amount of 2-hydroxy-3-naphthohydroxamic acid is used instead of the water glass inhibitor in Example 1 to add to the fluorocarbon cerium ore roughing, and finally a flotation concentrate (grade 48%) and a flotation tailings (grade 9%) are obtained.

[0069] Comparative Example 2

[0070] The only difference from Example 1 is that, in the application of the composite collector, only the 2-hydroxy-3-naphthohydroxamic acid and the water glass inhibitor in the amount of Example 1 are added, and 3-hydroxy-2-naphthoyl hydrazide is not added, and an equal amount of 2-hydroxy-3-naphthohydroxamic acid is used to replace the 3-hydroxy-2-naphthoyl hydrazide in Example 1 and added to the fluorocarbon cerium ore roughing, and finally a flotation concentrate (grade 45%) and a flotation tailings (grade 12%) are obtained.

[0071] Comparative Example 3

[0072] The only difference from Example 1 is that, in the application of the composite collector, only 3-hydroxy-2-naphthoyl hydrazide in the amount of Example 1 is added, and 2-hydroxy-3-naphthohydroxamic acid and water glass inhibitor are not added, and an equal amount of 3-hydroxy-2-naphthoyl hydrazide is used instead of 2-hydroxy-3-naphthohydroxamic acid and water glass inhibitor in Example 1 to add to the fluorocarbon cerium ore roughing, and finally a flotation concentrate (grade 40%) and a flotation tailings (grade 15%) are obtained.

[0073] Table 1 Flotation results of Examples 1-9 and Comparative Examples 1-3

[0074]

[0075] Combined with the data in Table 1, it shows that the flotation efficiency of the composite collector composed of 2-hydroxy-3-naphthohydroxamic acid and 3-hydroxy-2-naphthoylhydrazide is significantly improved compared with the use of a single collector. The REO content in the concentrate after flotation is ≥61.5wt%, and the recovery rate is ≥50%; the REO content in the flotation tailings is ≤8wt%.

[0076] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A rare earth mineral composite collector, characterized in that: It comprises 2-hydroxy-3-naphthohydroxamic acid and 3-hydroxy-2-naphthoylhydrazide; the mass ratio of the 2-hydroxy-3-naphthohydroxamic acid to the 3-hydroxy-2-naphthoylhydrazide is (3-9):

1.

2. A rare earth mineral composite collector, characterized in that: It comprises 2-hydroxy-3-naphthohydroxamic acid and 3-hydroxy-2-naphthoylhydrazide; the mass ratio of the 2-hydroxy-3-naphthohydroxamic acid to the 3-hydroxy-2-naphthoylhydrazide is (4-5):

1.

3. The rare earth mineral composite collector according to claim 1, characterized in that: The 3-hydroxy-2-naphthoic acid hydrazide is prepared by the following steps: 3-hydroxy-2-naphthoic acid methyl ester and hydrazine hydrate are mixed in a molar ratio of (0.8-2):1, and then reacted at a temperature of 60-90°C.

4. The rare earth mineral composite collector according to claim 3, characterized in that: The 3-hydroxy-2-naphthoic acid methyl ester and the hydrazine hydrate are mixed, and then reacted at a temperature of 80-85° C. to obtain the product.

5. The rare earth mineral composite collector according to claim 1, characterized in that: The 2-hydroxy-3-naphthohydroxamic acid is prepared by the following steps: 3-hydroxy-2-naphthoic acid methyl ester, hydroxylamine hydrochloride and NaOH solution are mixed, and then reacted at a temperature of 0-50°C.

6. The rare earth mineral composite collector according to claim 5, characterized in that: The 3-hydroxy-2-naphthoic acid methyl ester, the hydroxylamine hydrochloride and the NaOH solution are mixed, and then reacted at a temperature of 25-30° C. to obtain the product.

7. A method for preparing a rare earth mineral composite collector according to any one of claims 1 to 6, characterized in that: The 2-hydroxy-3-naphthohydroxamic acid and the 3-hydroxy-2-naphthoylhydrazide are mixed to obtain the rare earth mineral composite collector.

8. Use of the rare earth ore composite collector according to any one of claims 1 to 6 or the rare earth ore composite collector prepared by the preparation method according to claim 7 in bastnaesite flotation, characterized in that: The rare earth ore composite collector and inhibitor are added to the bastnaesite roughing process for flotation.

9. The use according to claim 8, characterized in that: The amount of rare earth ore composite collector added to each ton of fluorocarbon cerium ore for flotation is 32-34 kg; and / or, the inhibitor is one or more of water glass, alum, sodium fluorosilicate, carboxymethyl cellulose and citric acid.

Images