A composite flotation reagent for fluorite-type lepidolite ore and application thereof

Abstract

The application discloses a composite flotation reagent for fluorite-type lepidolite ore and application thereof. The reagent comprises a cationic collector and an anionic collector; the cationic collector comprises a morpholine type reagent and an amine type reagent; the anionic collector comprises a fatty acid type reagent; the mass ratio of the cationic collector to the anionic collector is 100-300:50-200; and the mass ratio of the morpholine type reagent to the amine type reagent in the cationic collector is 50-100:100-200. Based on the reagent provided by the application, the fluorite-type lepidolite ore can be recovered, the recovery rate of the fluorite-type lepidolite and the grade of the lepidolite concentrate can be remarkably improved, the process is simple, the cost is low, and the application is suitable for industrialization.

Description

Technical Field

[0001] This invention relates to a composite flotation reagent for lepidolite ore, specifically a composite flotation reagent for fluorite-type lepidolite ore and its application, belonging to the field of mineral processing technology. Background Technology

[0002] In the complex flotation system of lepidolite, researchers have found that single collectors for lepidolite suffer from problems such as large dosage, poor adaptability to temperature and slime, and low concentrate quality. However, combining multiple collectors often improves these issues and increases the collection efficiency of lepidolite. Due to the complexity of the flotation system, anionic fatty acid collectors can only collect activated lepidolite; unactivated lepidolite is almost impossible to float. Cationic amine collectors have good collection ability for lepidolite over a wide pH range, but their selectivity is not ideal. Combined anionic and cationic collectors, utilizing the synergistic effect of the reagents, can effectively improve the grade and recovery rate of lepidolite concentrate. Meanwhile, anionic collectors, especially fatty acid collectors, are commonly used in the industry for the effective flotation of fluorite, but they tend to cause preferential flotation of fluorite. Amine reagents have drawbacks in foam transport; the foam produced during flotation is sticky, difficult to defoam, and prone to entrainment problems.

[0003] Therefore, designing an efficient, simple, economical and feasible beneficiation method for fluorite-type lepidolite ore is of great practical significance for the comprehensive utilization of lepidolite resources. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the first objective of this invention is to provide a composite flotation reagent for fluorite-type lepidolite ore. This flotation reagent uses a composite collector formed by a cationic collector containing morpholine-based reagents and anionic collectors as the flotation reagent. By utilizing the synergistic effect of the two, the surface tension of the solution and the critical micelle concentration of the collector are reduced, thereby improving the activity of the reagent. This avoids the disadvantages of single-property collectors while also improving the selectivity and collection ability of the composite collector for fluorite-type lepidolite, greatly improving the grade and recovery rate of lepidolite concentrate.

[0005] The second objective of this invention is to provide an application of a composite flotation reagent for fluorite-type lepidolite ore, used for the recovery of fluorite-type lepidolite ore. The composite flotation reagent provided by this invention can significantly improve the recovery efficiency of lepidolite ore, and the process is simple, low-cost, and suitable for industrial application.

[0006] To achieve the above technical objectives, this invention provides a composite flotation reagent for fluorite-type lepidolite ore, comprising a cationic collector and an anionic collector; the cationic collector comprises morpholine-based reagents and amine-based reagents; the anionic collector comprises fatty acid-based reagents; the mass ratio of the cationic collector to the anionic collector is 100–300:50–200; and the mass ratio of the morpholine-based reagent to the amine-based reagent in the cationic collector is 50–100:100–200.

[0007] As a preferred embodiment, the morpholine agent is an alkylmorpholine; the alkylmorpholine is at least one of hexadecylmorpholine, 4-dodecyl-2,6-dimethylmorpholine, and octadecylmorpholine.

[0008] As a preferred embodiment, when the alkylmorpholine is hexadecylmorpholine, 4-dodecyl-2,6-dimethylmorpholine, and octadecylmorpholine, the mass ratio of the three is 60-80:5-20:5-30. More preferably, the mass ratio of hexadecylmorpholine, 4-dodecyl-2,6-dimethylmorpholine, and octadecylmorpholine is 70-80:10-15:10-15.

[0009] As a preferred embodiment, the amine agent is one of dodecylamine, octadecylamine, etheramine, and quaternary ammonium salt.

[0010] As a preferred embodiment, the fatty acid agent is one of oleic acid, oxidized paraffin soap, tal oil, and naphthenic acid.

[0011] Because fluorite-type lepidolite minerals contain fluorite, the conventional separation process involves increasing the dosage of amine reagents to prevent the preferential flotation of fluorite caused by fatty acid reagents, thus ensuring the grade of the lepidolite concentrate. This is mainly because the adsorption of amine reagents on the fluorite surface is generated by electrostatic interaction, which is greatly affected by the collector concentration and the hydrogen ion concentration in the pulp. When the pulp pH is neutral or weakly acidic, the selectivity of amine collectors for fluorite is poor. Therefore, increasing the dosage of amine reagents can prevent the preferential flotation of fluorite caused by fatty acid reagents. However, excessive dosage of amine reagents can lead to problems such as sticky foam and difficulty in defoaming.

[0012] This invention utilizes a composite collector, consisting of a cationic collector containing morpholine-based reagents and anionic collectors, as a flotation reagent. The cationic and anionic collectors exhibit a synergistic effect (1+1>2), effectively improving the grade and recovery rate of lepidolite concentrate. The synergistic effect between the cationic and anionic composite collectors reduces the surface tension of the solution and the critical micelle concentration of the collector, improving reagent activity and avoiding the drawbacks of single-property collectors, thus enhancing the selectivity and collection ability of the composite collector for lepidolite. Furthermore, while maintaining flotation separation efficiency, it reduces the dosage of amine reagents, effectively avoiding the drawbacks of amine reagents such as sticky foam and difficulty in defoaming, improving flotation separation efficiency, reducing foam volume, and solving the foam transport problem during the flotation process.

[0013] This invention also provides an application of a composite flotation reagent for fluorite-type lepidolite ore, used to recover fluorite-type lepidolite ore. The process is as follows: after grinding the raw fluorite-type lepidolite ore, a composite flotation reagent is added for roughing flotation to obtain lepidolite rough concentrate and rough tailings; the lepidolite rough concentrate is then subjected to flotation cleaning to obtain lepidolite concentrate and middlings; the rough tailings are then subjected to scavenging flotation with the composite flotation reagent to obtain lepidolite scavenging concentrate and scavenging tailings.

[0014] As a preferred embodiment, the amount of composite flotation reagent added in the roughing stage is 0.25 to 0.5 wt‰ of the fluorite-type lepidolite ore, wherein the mass ratio of cationic collector to anionic collector is 150 to 300: 100 to 200.

[0015] As a preferred embodiment, the amount of composite flotation reagent added in the scavenging stage is 0.20 to 0.30 wt‰ of the fluorite-type lepidolite ore, wherein the mass ratio of cationic collector to anionic collector is 100 to 200: 50 to 100.

[0016] As a preferred embodiment, the roughing process also uses an acid solution as a pH adjuster to adjust the pH of the roughing process to 5-7.

[0017] As a preferred embodiment, the coarse selection process takes 2 to 3 minutes.

[0018] As a preferred option, the selection process is a blank selection, which takes 3 to 4 minutes.

[0019] As a preferred embodiment, the scanning process takes 2 to 3 minutes.

[0020] As a preferred embodiment, the proportion of the fluorite-type lepidolite ore ground to a fine particle size of -0.074 mm is 55-65 wt%.

[0021] As a preferred embodiment, the grinding process of the fluorite-type lepidolite ore is wet grinding, with a liquid-to-solid ratio of 1:1 to 4. More preferably, the liquid-to-solid ratio is 1:2.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1) A composite collector, consisting of a cationic collector containing morpholine-based reagents and anionic collectors, is used as a flotation reagent. The synergistic effect of the two (1+1>2) is utilized to reduce the surface tension of the solution and the critical micelle concentration of the collector, thereby improving the activity of the reagent and avoiding the disadvantages of single-property collectors. At the same time, the selectivity and collection ability of the composite collector for fluorite-type lepidolite are improved, which greatly improves the grade and recovery rate of lepidolite concentrate.

[0024] 2) The adsorption of amine collectors on the surface of fluorite is generated by electrostatic interaction, and therefore is greatly affected by the concentration of collectors and the concentration of hydrogen ions in the pulp. When the pulp pH is neutral or weakly acidic, the selectivity of amine collectors for fluorite is poor. Therefore, increasing the dosage of amine collectors can effectively prevent fluorite from preferentially floating due to fatty acid-based agents.

[0025] 3) While ensuring the flotation separation effect, reducing the amount of amine reagents can effectively avoid the disadvantages of amine reagents such as sticky foam and difficulty in defoaming, improve the flotation separation effect, reduce the amount of foam, solve the problem of foam transportation in the flotation process, and achieve high separation efficiency, thereby increasing the grade of lepidolite concentrate and increasing the recovery rate. Attached Figure Description

[0026] Figure 1 This invention provides a process flow for recovering lepidolite from fluorite-type lepidolite ore. Detailed Implementation

[0027] The present invention will be further described below with reference to the accompanying drawings and specific preferred embodiments, but this does not limit the scope of protection of the present invention. All materials and instruments used in the following embodiments are commercially available.

[0028] The lepidolite ore used in this embodiment of the invention is a fluorite-type associated lepidolite ore from a certain place in Hunan Province. The main minerals are fluorite, lepidolite, quartz, muscovite, etc., and the mass percentage of Li2O is 0.36%.

[0029] Example 1

[0030] The following is a method for improving the recovery rate of fluorite-type lepidolite ore, which specifically includes the following steps:

[0031] (1) Grinding of fluorite-type lepidolite ore: For each ton of ore, based on dry weight, lepidolite ore (mineral sample) and water are added to the grinding mill for grinding at a liquid-to-solid ratio of 1:2 until the grinding fineness is -0.074mm, accounting for 60%.

[0032] (2) The slurry is subjected to flotation roughing, specifically: the above slurry is fed into the flotation machine, and dilute sulfuric acid, dodecylamine, HS and alkylmorpholine are added for flotation roughing. The amount of dilute sulfuric acid is 800 g / t, the amount of dodecylamine is 200 g / t, and the amount of HS is 200 g / t. The dodecylamine and HS are mixed and added to the flotation machine as a composite collector. The amount of alkylmorpholine is 100 g / t, and lepidolite flotation rough concentrate and roughing tailings are obtained.

[0033] (3) To perform flotation cleaning of the rough concentrate, specifically: feed the rough concentrate into the flotation machine and perform blank cleaning without adding flotation reagents to obtain lepidolite concentrate and middlings.

[0034] (4) The roughing tailings are subjected to flotation scavenging, specifically: the roughing tailings are fed into the flotation machine, flotation reagents are added for flotation scavenging, the reagents are dodecylamine, HS and alkylmorpholine, the amount of dodecylamine is 100g / t, the amount of HS is 100g / t, the dodecylamine and HS are mixed and added to the flotation machine as a composite collector, the amount of alkylmorpholine is 50g / t, and lepidolite scavenging concentrate and tailings are obtained.

[0035] Following the above process, lepidolite ore (the average mass percentage of Li2O in these raw ores was 0.36%) was recovered multiple times, and the average recovery results are shown in Table 1.

[0036] Table 1. Test Results of Example 1

[0037]

[0038] As shown in Table 1, in Example 1, after processing with the beneficiation process of the present invention, the Li2O grade in the obtained lepidolite concentrate was increased to 1.21%, and the Li2O recovery rate was 93.23%. Clearly, the beneficiation process of the present invention can separate lithium minerals from the fine mud in lepidolite ore, achieving effective resource recovery and having broad practical significance for improving the comprehensive utilization rate of lepidolite resources.

[0039] Example 2

[0040] The following is a method for improving the recovery rate of fluorite-type lepidolite ore, which specifically includes the following steps:

[0041] (1) The test ore sample was taken from a fluorite-type lepidolite mine in Chenzhou. It was ground. Specifically, for each ton of raw ore, based on dry weight, the lepidolite ore (ore sample) and water were added to the grinding mill at a liquid-to-solid ratio of 1:2 until the grinding fineness was -0.074mm, accounting for 60%.

[0042] (2) The slurry is subjected to flotation roughing, specifically: the above slurry is fed into the flotation machine, and dilute sulfuric acid, dodecylamine, HS and hexadecylmorpholine are added for flotation roughing. The amount of dilute sulfuric acid is 800 g / t, the amount of dodecylamine is 200 g / t, the amount of HS is 250 g / t and the amount of hexadecylmorpholine is 100 g / t relative to the fluorite-type lepidolite ore. The dodecylamine, hexadecylmorpholine and HS are mixed and added to the flotation machine as a composite collector to obtain lepidolite flotation rough concentrate and roughing tailings.

[0043] (3) To perform flotation cleaning of the rough concentrate, specifically: feed the rough concentrate into the flotation machine and perform blank cleaning without adding flotation reagents to obtain lepidolite concentrate and middlings.

[0044] (4) The roughing tailings are subjected to flotation scavenging, specifically: the roughing tailings are fed into the flotation machine, flotation reagents are added for flotation scavenging, the reagents are dodecylamine, HS, and hexadecylmorpholine, the amount of dodecylamine is 100g / t, the amount of HS is 125g / t, and the amount of alkylmorpholine is 50g / t. The dodecylamine, hexadecylmorpholine and HS are mixed and added to the flotation machine as a composite collector to obtain lepidolite scavenging concentrate and tailings.

[0045] Following the above process, lepidolite ore (the average mass percentage of Li2O in these raw ores was 0.36%) was recovered multiple times, and the average recovery results are shown in Table 2.

[0046] Table 2. Experimental Results of Example 2

[0047]

[0048] As shown in Table 2, in Example 2, after processing with the beneficiation process of the present invention, the Li2O grade in the obtained lepidolite concentrate was increased to 1.23%, and the Li2O recovery rate was 68.78%. Clearly, the beneficiation process of the present invention can separate lithium minerals from the fine mud in lepidolite ore, achieving effective resource recovery and having broad practical significance for improving the comprehensive utilization rate of lepidolite resources.

[0049] Comparative Example 1

[0050] The ore and method of Example 1 are used to recover lepidolite ore, except that no morpholine-based reagents are added.

[0051] Specific mineral processing test indicators are shown in Table 2.

[0052] Table 2 Results of Comparative Example 1

[0053]

[0054] As shown in Table 2, without the addition of morpholine-based reagents, the grade and recovery rate of the lithium concentrate obtained were significantly lower than the experimental indicators of Example 1.

[0055] Comparative Example 2

[0056] The ore and method of Example 1 are used to recover lepidolite ore, except that no amine reagents are added, and morpholine reagents are used instead of dodecylamine.

[0057] Specific mineral processing test indicators are shown in Table 4.

[0058] Table 4. Results of Comparative Example 2

[0059]

[0060] As shown in Table 4, when only morpholine-based reagents are added in combination with HS, the grade and recovery rate of the lithium concentrate obtained are significantly lower than the test indicators of Example 1.

[0061] 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 many possible variations and modifications to the technical solutions of the present invention using the methods and techniques disclosed above, or modify them into equivalent embodiments with equivalent changes, without departing from the spirit and technical essence of the present invention. Therefore, any simple modifications, equivalent substitutions, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solutions of the present invention shall still fall within the protection scope of the technical solutions of the present invention.

Claims

1. The application of a composite flotation reagent for fluorite-type lepidolite ore, characterized in that: The composite flotation reagent includes a cationic collector and an anionic collector; the cationic collector includes morpholine-based reagents and amine-based reagents; the anionic collector includes fatty acid-based reagents; the mass ratio of the cationic collector to the anionic collector is 100~300:50~200; and the mass ratio of the morpholine-based reagent to the amine-based reagent in the cationic collector is 50~100:100~200. The composite flotation reagent is used to recover fluorite-type lepidolite ore. The process is as follows: after grinding the fluorite-type lepidolite ore, the composite flotation reagent is added for roughing flotation to obtain lepidolite rough concentrate and rough tailings; the lepidolite rough concentrate is then subjected to fine flotation to obtain lepidolite concentrate and middlings. The roughing tailings are added with composite flotation reagents for flotation scavenging to obtain lepidolite scavenged concentrate and scavenged tailings.

2. The application of the composite flotation reagent for fluorite-type lepidolite ore according to claim 1, characterized in that: The morpholine-based drug is an alkylmorpholine; the alkylmorpholine is at least one of hexadecylmorpholine, 4-dodecyl-2,6-dimethylmorpholine, and octadecylmorpholine.

3. The application of the composite flotation reagent for fluorite-type lepidolite ore according to claim 2, characterized in that: When the alkylmorpholine is hexadecylmorpholine, 4-dodecyl-2,6-dimethylmorpholine, and octadecylmorpholine, the mass ratio of the three is 60~80:5~20:5~30.

4. The application of the composite flotation reagent for fluorite-type lepidolite ore according to claim 1, characterized in that: The amine agent is one of dodecylamine, octadecylamine, etheramine, and quaternary ammonium salt; the fatty acid agent is one of oleic acid, oxidized paraffin soap, tal oil, and naphthenic acid.

5. The application of the composite flotation reagent for fluorite-type lepidolite ore according to claim 1, characterized in that: The amount of composite flotation reagent added in the roughing stage is 0.25~0.5wt‰ of the fluorite-type lepidolite ore, wherein the mass ratio of cationic collector to anionic collector is 150~300:100~200.

6. The application of the composite flotation reagent for fluorite-type lepidolite ore according to claim 1, characterized in that: The amount of composite flotation reagent added in the scavenging stage is 0.20~0.30wt‰ of the fluorite-type lepidolite ore, wherein the mass ratio of cationic collector to anionic collector is 100~200:50~100.

7. The application of the composite flotation reagent for fluorite-type lepidolite ore according to claim 1, characterized in that: The roughing process also uses an acid solution as a pH adjuster to adjust the pH of the roughing process to 5-7; the roughing process takes 2-3 minutes.

8. The application of the composite flotation reagent for fluorite-type lepidolite ore according to claim 1, characterized in that: The selection process is a blank selection, which takes 3-4 minutes; the scanning process takes 2-3 minutes.

9. The application of the composite flotation reagent for fluorite-type lepidolite ore according to claim 1, characterized in that: The proportion of the fluorite-type lepidolite ore ground to a fine particle size of -0.074 mm is 55~65 wt%.

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