Composite collecting agent for rare earth ore and application of composite collecting agent in flotation

Abstract

The invention provides a composite collecting agent for rare earth ore and application of the composite collecting agent in flotation, and relates to the technical field of rare earth flotation. The composite collecting agent is prepared from hydroxamic acid organic matter, ether organic matter and phosphate organic matter according to the mass ratio of (15-20): (3-8): (1-3). When the composite collecting agent is applied to flotation, after rare earth ore is crushed and ground, the rare earth composite collecting agent, an inhibitor and a foaming agent are sequentially added into ore pulp for flotation under the set ore pulp concentration, temperature and pH. When the composite collecting agent is applied to separation of rare earth minerals and gangue minerals, the main agent hydroxamic acid organic matter is selectively combined with metal ions on the surfaces of the rare earth minerals, selective separation of the rare earth minerals and gangue is achieved, the auxiliary agent ethers enhance the solubility of hydroxamic acid, the dosage of the hydroxamic acid is reduced, and the recovery rate of the gangue minerals is increased. The auxiliary agent phosphate reinforced hydroximic acid is used for recycling the rare earth ore, foam is improved, and the grade and the recycling rate of the rare earth ore concentrate are improved.

Description

Technical Field

[0001] The invention relates to the technical field of rare earth flotation, in particular to a composite collector for rare earth ore and its application in flotation. Background Art

[0002] Due to their unique spatial structure and physical and chemical properties, rare earth elements are widely used in important fields such as high-end manufacturing, artificial intelligence, aerospace, and national defense. They are key raw materials for pillar and leading industries and are known as "industrial vitamins." Fluorocarbon cerium ore, monazite, etc. are the main minerals containing rare earth elements, and they often coexist with calcium-containing minerals such as fluorite and dolomite. Flotation is the most common method for separating rare earth minerals from calcium-containing minerals, but because the floatability of the two is similar, separation is difficult. At the same time, due to the activation and mechanical entrainment of metal ions during the flotation process, silicate minerals such as quartz, amphibole and feldspar float up, which reduces the grade of rare earth concentrate.

[0003] At present, hydroxamic acid or fatty acid is commonly used as a collector in industry, and water glass is used as a gangue inhibitor. However, hydroxamic acid has low solubility and high reagent consumption. Fatty acid has high flotation foam viscosity and poor merging effect due to the characteristics of the reagent, which makes flotation foam entrainment serious. At the same time, water glass has an unsatisfactory inhibitory effect on calcium-containing minerals. Therefore, it is of great significance to develop a collector with high solubility and low foam viscosity that is selective for rare earth minerals and a selective inhibitor for calcium-containing minerals. Summary of the invention

[0004] In order to solve the above technical problems existing in the prior art, the embodiment of the present invention provides a composite collector for rare earth ores and its application in flotation. The technical solution is as follows:

[0005] A composite collector for rare earth ores, obtained by mixing hydroxamic acid organic matter, ether organic matter and phosphate organic matter in a mass ratio of 15-20:3-8:1-3;

[0006] The hydroxamic acid organic compound is two or more of 1-hydroxy-2-naphthohydroxamic acid, 2-hydroxy-3-naphthohydroxamic acid, benzohydroxamic acid, p-tert-butylbenzohydroxamic acid, cycloalkanehydroxamic acid, and octylhydroxamic acid;

[0007] The ether organic matter is one or more of alkylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, tristyrylphenol polyoxyethylene ether;

[0008] The phosphate organic matter is one or more of tributyl phosphate and triisobutyl phosphate.

[0009] When the composite collector is used in flotation, specifically, after the rare earth ore is crushed and ground to a certain fineness, the rare earth composite collector, inhibitor and bubbling agent are sequentially added to the pulp at a suitable pulp concentration, temperature and pH to carry out flotation.

[0010] The rare earth ore is one or more of bastnaesite, monazite, xenotime, bastnaesite and natronite.

[0011] The grinding to -0.074 mm accounts for 70% to 98%, the mass concentration of the slurry is 40% to 70%, the pH value of the slurry is 7 to 11, and the slurry temperature is 45 to 70° C. The pH of the slurry is adjusted by adding sodium carbonate and / or sodium hydroxide.

[0012] The added amount of the composite collector is 0.6-2.0 Kg / t.

[0013] The inhibitor is added in an amount of 0.5-1.5 kg / t, and is a composite inhibitor prepared by mixing water glass, organic acids and hydroxyethyl cellulose in a mass ratio of 5-9:0.5-3:0.5-2.

[0014] The organic acid is one or more of oxalic acid, citric acid, ethylenediaminetetraacetic acid, gallic acid and tartaric acid.

[0015] The amount of the foaming agent added is 50-200 g / t. Conventional foaming agents can be used as the foaming agent, and preferably, 2# oil is used as the foaming agent.

[0016] During the process of adding the composite collector and the inhibitor to the ore pulp, when adding the composite collector, the hydroxamic acid organic matter and the ether organic matter are first mixed evenly and then added to the ore pulp, and then the phosphate organic matter is added to the ore pulp; when adding the inhibitor, the water glass, organic acids and hydroxyethyl cellulose are mixed evenly and then added to the ore pulp.

[0017] The gangue minerals in the above rare earth ores are mainly calcium-containing minerals and silicate gangue minerals, wherein the calcium-containing minerals are one or more of fluorite, dolomite, apatite and calcite; and the silicate gangue minerals are one or more of quartz, feldspar, amphibole and nepheline.

[0018] The beneficial effects brought about by the technical solution provided by the embodiment of the present invention include at least:

[0019] (1) When the composite collector of the present invention is used for separating rare earth minerals from gangue minerals, the main agent hydroxamic acid organic matter can selectively combine with metal ions on the surface of rare earth minerals, thereby realizing the selective separation of rare earth minerals from gangue minerals, the auxiliary agent ether can enhance the solubility of hydroxamic acid and reduce the amount of hydroxamic acid used, and the auxiliary agent phosphate can enhance the recovery of hydroxamic acid on rare earth minerals and improve foam annealing. The synergistic effect of the three agents greatly improves the grade and recovery rate of rare earth concentrates, and the effect is better than that of a single hydroxamic acid collector.

[0020] (2) In the flotation process of rare earth ores, the inhibitor composed of water glass, organic acids and hydroxyethyl cellulose has a strong inhibitory ability against both calcium-containing minerals and silicate minerals, and has better selectivity for calcium-containing gangue minerals than selecting only water glass.

[0021] (3) The composite collector and composite depressant selected in the flotation process of rare earth ores of the present invention have strong adaptability to various ores, small dosage, low cost, and have the potential for large-scale promotion. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0023] Figure 1 The present invention provides a process flow chart of the application of a composite collector for rare earth ores in flotation. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is described below in conjunction with the accompanying drawings.

[0025] In the embodiments of the present invention, words such as "exemplarily" and "for example" are used to indicate examples, illustrations or explanations. Any embodiment or design described as "example" in the present invention should not be interpreted as being more preferred or more advantageous than other embodiments or designs. Specifically, the use of the word "example" is intended to present the concept in a specific way. In addition, in the embodiments of the present invention, the meaning expressed by "and / or" can be both, or it can be either of the two.

[0026] In the embodiments of the present invention, sometimes the subscripts such as W 1 It may be written in non-subscript form such as W1. When the difference is not emphasized, the meaning is the same.

[0027] In order to make the technical problems, technical solutions and advantages to be solved by the present invention more clear, a detailed description will be given below with reference to the accompanying drawings and specific embodiments.

[0028] The embodiment of the present invention provides a composite collector for rare earth ores and application thereof in flotation.

[0029] The collector is prepared by mixing hydroxamic acid organic matter, ether organic matter and phosphate organic matter in a mass ratio of 15-20:3-8:1-3;

[0030] The hydroxamic acid organic compound is two or more of 1-hydroxy-2-naphthohydroxamic acid, 2-hydroxy-3-naphthohydroxamic acid, benzohydroxamic acid, p-tert-butylbenzohydroxamic acid, cycloalkanehydroxamic acid, and octylhydroxamic acid;

[0031] The ether organic matter is one or more of alkylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, tristyrylphenol polyoxyethylene ether;

[0032] The phosphate organic matter is one or more of tributyl phosphate and triisobutyl phosphate.

[0033] like Figure 1 The flow chart shown is for the application of the composite collector for rare earth ore in flotation, specifically, after the rare earth ore is crushed and ground to a certain fineness, the rare earth composite collector, inhibitor and bubbling agent are added to the slurry in sequence at a suitable slurry concentration, temperature and pH for flotation.

[0034] This will be described below with reference to specific embodiments.

[0035] Example 1

[0036] The composite collector of the present invention comprises hydroxamic acid organic matter, dodecylphenol polyoxyethylene ether and tributyl phosphate in a mass ratio of 16:5:1.5, wherein the hydroxamic acid organic matter comprises 9 parts of 1-hydroxy-2-naphthohydroxamic acid, 5 parts of p-tert-butylbenzohydroxamic acid and 2 parts of cycloalkanehydroxamic acid (by mass).

[0037] The composite depressant of this embodiment is applied to the flotation process of a rare earth mine in Inner Mongolia (REO grade is 6.45%, rare earth minerals are mainly fluorocarbon cerium and monazite, and gangue is mainly fluorite, dolomite, amphibole and nephrite), and its process flow chart is as follows: Figure 1 As shown, the specific process is as follows:

[0038] First, the rare earth ore is ground to -0.074mm with a mass ratio of 95%, the pulp concentration is 60%, and the flotation temperature is 60℃. Then, sodium carbonate is used to adjust the pulp pH to 9.5, and a composite inhibitor (a mixture of water glass, ethylenediaminetetraacetic acid and hydroxyethyl cellulose with a mass ratio of 6:3:1) and a composite collector (a mixture of hydroxamic acid organic matter and dodecylphenol polyoxyethylene ether is added first, and then tributyl phosphate is added. The reagents of the composite collector in the subsequent process need to be added according to this step). After one roughing, three fines and one sweeping (the dosage of the roughing composite inhibitor is 1.5Kg / t, the dosage of the composite collector is 0.8Kg / t, starting from The dosage of foaming agent 2# oil is 110g / t; the dosage of composite depressant for refinement 1 is 0.5Kg / t, that for refinement 2 is 0.25Kg / t, and that for refinement 3 is 0.1Kg / t; the dosage of composite collector for refinement 1 is 0.2Kg / t, that for refinement 2 is 0.1Kg / t, and that for refinement 3 is blank selection; the dosage of foaming agent 2# oil for refinement 2 is 20g / t; the dosage of composite collector for sweeping 1 is 0.3Kg / t, and that of foaming agent 2# oil is 30g / t). After the closed-circuit flotation process with sequential return of the middlings, the REO grade in the rare earth concentrate obtained is 60.14%, and the recovery rate is 62.57%; the CaO content is 5.13%, and the recovery rate is 2.21%; the SiO 2 Content 0.64%, recovery rate 0.96%.

[0039] Comparative Example 1:

[0040] The flotation steps of this comparative example are consistent with those of Example 1, except that the composite depressant and the composite collector in Example 1 are replaced by equal amounts of water glass and 1-hydroxy-2-naphthohydroxamic acid. The REO grade and recovery rate in the final rare earth concentrate are 56.36% and 50.54% respectively; the CaO content is 11.06% and the recovery rate is 3.81%; the SiO 2 The content is 0.95% and the recovery rate is 1.44%. By comparing the test results, it can be seen that the REO grade and recovery rate in this comparative example, especially the recovery rate, are much lower than those in Example 1, and the SiO content in the rare earth concentrate is 0.95%. 2 and CaO content, especially the CaO content is also much higher than that of Example 1, indicating that the flotation effect of the rare earth ore composite depressor and composite collector in the flotation process is significantly better than that of the single depressor water glass and the single collector hydroxamic acid.

[0041] Comparative Example 2:

[0042] The flotation steps of this comparative example are consistent with those of Example 1, except that the composite collector in Example 1 is replaced with an equal amount of 1-hydroxy-2-naphthohydroxamic acid collector. The REO grade and recovery rate in the final rare earth concentrate are 58.24% and 53.18%, respectively; the CaO content is 9.06%, and the recovery rate is 3.31%; the SiO 2The content is 0.82% and the recovery rate is 1.15%. The REO grade in this comparative example is lower than that in Example 1, and the REO recovery rate is significantly lower than that in Example 1. 2 The contents are higher than those in Example 1, which indicates that the flotation effect of the composite collector used in the flotation process is significantly better than that of the single 1-hydroxy-2-naphthohydroxamic acid.

[0043] Comparative Example 3:

[0044] The flotation steps of this comparative example are the same as those of Example 1, except that the composite depressant in Example 1 is replaced with an equal amount of water glass. The REO grade and recovery rate in the final rare earth concentrate are 59.21% and 58.54% respectively; the CaO content is 8.73% and the recovery rate is 2.95%; the SiO 2 The content is 0.66% and the recovery rate is 0.94%. By comparing the test results, it can be seen that the REO grade and recovery rate in this comparative example are lower than those in Example 1, and the SiO content in the rare earth concentrate is 0.66%. 2 The content of CaO is also much higher than that of Example 1, which indicates that the flotation effect of the rare earth ore composite depressant in the flotation process is significantly better than that of single water glass.

[0045] Comparative Example 4:

[0046] The flotation steps of this comparative example are consistent with those of Example 1, except that all reagents in the composite collector of Example 1 are mixed uniformly before being added to the slurry. The REO grade and recovery rate in the final rare earth concentrate are 49.33% and 37.19% respectively; the CaO content is 13.68% and the recovery rate is 4.37%; the SiO 2 The content of SiO in the rare earth concentrate is 1.88% and the recovery rate is 1.42%. By comparing the test results, it is found that the REO grade and recovery rate of the rare earth concentrate in Comparative Example 4 are lower than those in Example 1. 2 The CaO content is also much higher than that in Example 1, indicating that adding the composite collector after partial mixing is better than adding after all mixing. This may be because a chemical reaction occurs after all the composite collectors are mixed, producing components that are not conducive to the capture of rare earth minerals.

[0047] Example 2

[0048] The composite collector of the present invention comprises hydroxamic acid organic matter, tristyrylphenol polyoxyethylene ether and triisobutyl phosphate in a mass ratio of 18:3:2, wherein the hydroxamic acid organic matter comprises 10 parts of 2-hydroxy-3-naphthohydroxamic acid, 7 parts of benzohydroxamic acid and 1 part of octyl isohydroxamic acid (by mass).

[0049] The composite depressant of the present embodiment is applied to the flotation process of a rare earth ore in India (REO grade is 3.85%, the rare earth minerals are mainly fluorocarbon cerium ore and fluorocarbon calcium cerium ore, and the gangue is mainly calcite, apatite and feldspar). The specific process is as follows: first, the rare earth ore is ground to -0.074mm, the mass ratio is 80%, the pulp concentration is 65%, and the flotation temperature is 55°C. Then, the pulp pH is adjusted to 10 with sodium carbonate, and a composite depressant (a mixture of water glass, organic acid and hydroxyethyl cellulose with a mass ratio of 5:3:2, wherein the organic acid includes 2 parts of citric acid and 1 part of oxalic acid) and a composite collector (a mixture of hydroxamic acid organic matter and tristyrylphenol polyoxyethylene ether is added first, and then tributyl phosphate is added. In the subsequent process, the reagents of the composite collector need to be added according to this step). Four roughing and one refining sweep (the dosage of the composite depressor for roughing is 1.0Kg / t, the dosage of the composite collector is 1.2Kg / t, and the dosage of the frother 2# oil is 80g / t; the dosage of the composite depressor for refining is 0.6Kg / t, the dosage of refining 2 is 0.3Kg / t, the dosage of refining 3 is 0.15Kg / t, and the refining 4 is blank selection; the dosage of the composite collector for refining 1 is 0.3Kg / t, the refining 2 is blank selection, the dosage of refining 3 is 0.1Kg / t, and the refining 4 is blank selection; the dosage of the frother 2# oil for refining 3 is 10g / t; the dosage of the composite collector for sweeping 1 is 0.4Kg / t, and the frother 2# oil is 20g / t), after the closed-circuit flotation process with the middle ore returned in sequence, the REO grade in the obtained rare earth concentrate is 61.55%, and the recovery rate is 70.52%; the CaO content is 4.93%, and the recovery rate is 1.85%; SiO 2 Content 0.37%, recovery rate 1.14%.

[0050] Example 3

[0051] The composite collector of the present invention comprises hydroxamic acid organic matter, octylphenol polyoxyethylene ether and triisobutyl phosphate in a mass ratio of 15:6:1, wherein the hydroxamic acid organic matter comprises 10 parts of benzohydroxamic acid and 5 parts of cycloalkanehydroxamic acid.

[0052] The composite depressant of the present embodiment is applied to the flotation process of a rare earth ore in Australia (REO grade is 5.73%, the rare earth minerals are mainly xenotime, and the gangue is mainly quartz and amphibole). The specific process is as follows: first, the rare earth ore is ground to -0.074 mm, the mass ratio is 95%, the slurry concentration is 55%, and the flotation temperature is 50°C. Then, the pH value of the slurry is adjusted to 8.5 with sodium carbonate, and a composite depressant (a mixture of water glass, gallic acid and hydroxyethyl cellulose in a mass ratio of 8:0.5:1.5) and a composite collector (a mixture of hydroxamic acid organic matter and octylphenol polyoxyethylene ether is added first, and then tributyl phosphate is added. In the subsequent process, the reagents of the composite collector need to be added according to this step. After one roughing and three refining (the dosage of composite depressant in roughing is 0.6Kg / t, the dosage of composite collector is 1.8Kg / t, and the dosage of frother 2# oil is 150g / t; the dosage of composite depressant in refining is 0.2Kg / t, the dosage of refining is 0.1Kg / t, and the dosage of refining is 0.1Kg / t; the dosage of composite collector in refining is 0.6Kg / t, the dosage of refining is 0.2Kg / t, the dosage of refining is 0.1Kg / t, and the dosage of refining is 0.1Kg / t; the dosage of frother 2# oil in refining is 40g / t, and the dosage of refining is 10g / t), the middling ore is returned in sequence, the REO grade in the obtained rare earth concentrate is 54.15%, the recovery rate is 79.82%; the CaO content is 1.03%, the recovery rate is 0.49%; the SiO 2 Content 9.48%, recovery rate 3.66%.

[0053] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A composite collector for rare earth ores, characterized in that: The hydroxamic acid organic matter, the ether organic matter and the phosphate organic matter are mixed in a mass ratio of 15-20:3-8:1-3; The hydroxamic acid organic compound is two or more of 1-hydroxy-2-naphthohydroxamic acid, 2-hydroxy-3-naphthohydroxamic acid, benzohydroxamic acid, p-tert-butylbenzohydroxamic acid, cycloalkanehydroxamic acid, and octylhydroxamic acid; The ether organic matter is one or more of alkylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, tristyrylphenol polyoxyethylene ether; The phosphate organic matter is one or more of tributyl phosphate and triisobutyl phosphate.

2. The use of the composite collector for rare earth ores in flotation according to claim 1, characterized in that: After the rare earth ore is crushed and ground to a certain fineness, the rare earth composite collector, inhibitor and bubbling agent are sequentially added into the slurry at a suitable slurry concentration, temperature and pH value for flotation.

3. The use of the composite collector for rare earth ores in flotation according to claim 2, characterized in that: The rare earth ore is one or more of bastnaesite, monazite, xenotime, bastnaesite and natronite.

4. The use of the composite collector for rare earth ores in flotation according to claim 2, characterized in that: The grinding to -0.074 mm accounts for 70% to 98%, the mass concentration of the slurry is 40% to 70%, the pH value of the slurry is 7 to 11, and the temperature of the slurry is 45 to 70°C.

5. The use of the composite collector for rare earth ores in flotation according to claim 2, characterized in that: The added amount of the composite collector is 0.6-2.0 Kg / t.

6. The use of the composite collector for rare earth ores in flotation according to claim 2, characterized in that: The inhibitor is added in an amount of 0.5-1.5 kg / t, and is a composite inhibitor prepared by mixing water glass, organic acids and hydroxyethyl cellulose in a mass ratio of 5-9:0.5-3:0.5-2.

7. The use of the composite collector for rare earth ores in flotation according to claim 6, characterized in that: The organic acid is one or more of oxalic acid, citric acid, ethylenediaminetetraacetic acid, gallic acid and tartaric acid.

8. The use of the composite collector for rare earth ores in flotation according to claim 2, characterized in that: The added amount of the foaming agent is 50-200 g / t.

9. The use of the composite collector for rare earth ores in flotation according to claim 2, characterized in that: When the composite collector is added into the ore pulp, the hydroxamic acid organic matter and the ether organic matter are firstly mixed evenly and then added into the ore pulp, and then the phosphate organic matter is added into the ore pulp.

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