Flotation reagent and flotation method thereof

Abstract

The invention discloses a flotation reagent and a flotation method thereof. The flotation reagent comprises the following components in parts by weight: 30-50 parts of non-modified oleic acid; 10 to 15 parts of modified oleic acid; 15 to 30 parts of a sulfonic acid compound; 3-8 parts of a hydroxamic acid compound; 4 to 6.5 parts of an ether compound; 5-20 parts of esterified vegetable oil, and 10-30 parts of potassium hydroxide. The agent can improve the collecting capacity of a lithium ore flotation method and improve the selectivity.

Description

Technical Field

[0001] This invention relates to the field of metallurgical engineering technology, and in particular to a flotation reagent and a flotation method thereof. Background Technology

[0002] With the development of battery technology, lithium plays an increasingly important role in batteries. Currently, most industrially valuable spodumene can be processed using flotation. However, due to the poor floatability of lepidolite and petalite, their similar physicochemical properties, coupled with the presence of gangue minerals such as feldspar, quartz, and mica in the ore, separation becomes difficult. Conventional single flotation reagents suffer from insufficient collecting capacity, poor selectivity, and poor adaptability to ores with complex mineral compositions. Therefore, improving collecting capacity and selectivity has become an urgent problem to be solved. Summary of the Invention

[0003] This invention provides a flotation reagent and a flotation method thereof, which can improve the collection capacity and selectivity of lithium ore flotation.

[0004] This invention provides a flotation reagent comprising, by weight parts: unmodified oleic acid: 30-50 parts; modified oleic acid: 10-15 parts; sulfonic acid compounds: 15-30 parts; hydroxamic acid compounds: 3-8 parts; ether compounds: 4-6.5 parts; esterified vegetable oil: 5-20 parts; and potassium hydroxide: 10-30 parts.

[0005] Furthermore, the modified oleic acid includes one or more of sulfated oleic acid, sulfonated oleic acid, and esterified oleic acid; the esterified vegetable oil includes one or more of epoxidized soybean oleate methyl ester, epoxidized linseed oleate methyl ester, and phosphated castor oil ester.

[0006] Furthermore, the sulfonic acid compound includes at least one of sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sulfonated kerosene, and sodium petroleum sulfonate.

[0007] Furthermore, the hydroxamic acid compounds include at least one of benzohydroxyxamic acid, salicylic acid, C5-9 hydroxamic acid, and their sodium or potassium salts.

[0008] The present invention also provides a flotation method, which uses the above-mentioned flotation reagents to float lithium ore to be selected.

[0009] Furthermore, the method includes the following steps: S1: Prepare lithium ore slurry from the lithium ore to be selected; S2: Adjust the pH of the slurry to 7.5-10; S3: Add flotation reagent; S4: Perform coarse selection, sweep selection and fine selection in sequence.

[0010] Furthermore, the concentration of the slurry is 20%-40%.

[0011] Further, in step S2, the pH of the slurry is adjusted using a pH adjuster, which includes alkali metal carbonates and / or alkali metal hydroxides. The alkali metal carbonates are selected from one or more of potassium carbonate, sodium carbonate, and rubidium carbonate, and the alkali metal hydroxides are selected from one or more of potassium hydroxide and sodium hydroxide.

[0012] Furthermore, in step S3, the method also includes adding an activator, which includes sodium fluoride or an amino acid derivative, wherein the amino acid derivative includes one or more of monosodium glutamate, potassium glutamate, potassium glycinate, and copper glycinate.

[0013] Furthermore, the dosage of this activator is 50-600g per ton.

[0014] Further, in step S3, the method includes: heating unmodified oleic acid, modified oleic acid, and esterified vegetable oil to 60-70°C and mixing them uniformly; then adding a pre-prepared aqueous solution of potassium hydroxide to the mixture; stirring at 70-90°C for 1-2 hours, then cooling to 30-50°C; then adding sulfonic acid compounds, hydroxamic acid compounds, and ether compounds, stirring, cooling to room temperature, and diluting with water to a concentration of 40%-50%.

[0015] Furthermore, the amount of flotation reagent added to the lithium ore slurry is 150-900 g / t.

[0016] In summary, the flotation reagent system of this invention exhibits a significant synergistic effect: a significant synergistic effect occurs among the components. Industrial oleic acid provides basic collecting properties, modified oleic acid enhances surface activity, sulfonic acid compounds improve selectivity, hydroxamic acid compounds enhance foam stability, ether compounds improve dispersibility, esterified vegetable oil enhances low-temperature adaptability, and potassium hydroxide provides appropriate saponification. Therefore, this reagent can improve the collecting capacity and selectivity of lithium ore flotation.

[0017] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described in detail below. Detailed Implementation

[0018] To further illustrate the technical means and effects adopted by the present invention in order to achieve the intended purpose, the present invention will be described in detail below with reference to preferred embodiments.

[0019] This invention provides a flotation reagent and a flotation method thereof. The reagent is used in lithium ore flotation and can improve the collection capacity and selectivity of the lithium ore flotation method.

[0020] The flotation reagents provided in this embodiment of the invention comprise, by weight, the following: unmodified oleic acid: 30-50 parts; modified oleic acid: 10-15 parts; sulfonic acid compounds: 15-30 parts; hydroxamic acid compounds: 3-8 parts; ether compounds: 4-6.5 parts; esterified vegetable oil: 5-20 parts; and potassium hydroxide (KOH): 10-30 parts.

[0021] It should be mentioned that unmodified oleic acid is the opposite of modified oleic acid. Unmodified oleic acid is the general industrial oleic acid.

[0022] More specifically, in this embodiment, the modified oleic acid may include one or more of sulfated oleic acid, sulfonated oleic acid, and esterified oleic acid; preferably, the modified oleic acid includes sulfated vegetable oleic acid. Sulfonic acid compounds include at least one of sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sulfonated kerosene, and sodium petroleum sulfonate. Esterified vegetable oils include one or more of epoxidized soybean oleate methyl ester, epoxidized linseed oleate methyl ester, and phosphated castor oil ester.

[0023] The hydroxamic acid compound may include at least one of benzohydroxyxamic acid, salicylic acid, C5-9 hydroxamic acid and their sodium or potassium salts, preferably salicylic acid.

[0024] The present invention also provides a flotation method, the method comprising the following steps: S1: Prepare lithium ore slurry from the lithium ore to be selected.

[0025] In this embodiment, the concentration of the slurry can be 20%-40%.

[0026] S2: Adjust the pH of the slurry to 7.5-10; In this embodiment, a pH adjuster is used to adjust the pH of the slurry. The pH adjuster includes alkali metal carbonates and / or alkali metal hydroxides. The alkali metal carbonates are selected from one or more of potassium carbonate, sodium carbonate, and rubidium carbonate, and the alkali metal hydroxides are selected from one or more of potassium hydroxide and sodium hydroxide.

[0027] Furthermore, an activator may be added in this step. This activator can be sodium fluoride or an amino acid derivative, wherein the amino acid derivative is one or more of monosodium glutamate, potassium glutamate, potassium glycinate, and copper glycinate. The activator can be 50-600g per ton by weight.

[0028] S3: Add flotation reagent; The flotation reagents, by weight, include: unmodified oleic acid: 30-50 parts; modified oleic acid: 10-15 parts; sulfonic acid compounds: 15-30 parts; hydroxamic acid compounds: 3-8 parts; ether compounds: 4-6.5 parts; esterified vegetable oil: 5-20 parts; and potassium hydroxide (KOH): 10-30 parts.

[0029] More specifically, in this embodiment, the modified oleic acid may include one or more of sulfated oleic acid, sulfonated oleic acid, and esterified oleic acid; preferably, the modified oleic acid includes sulfated vegetable oleic acid. The sulfonic acid compound includes sodium dodecyl sulfonate. The esterified vegetable oil includes one or more of epoxidized soybean oleate methyl ester, epoxidized linseed oleate methyl ester, and phosphated castor oil ester.

[0030] Furthermore, in preparing the flotation reagent, unmodified oleic acid, modified oleic acid, and esterified vegetable oil can be heated to 60-70℃ and mixed uniformly; then, a pre-prepared potassium hydroxide aqueous solution is added to the mixture; the mixture is stirred at 70-90℃ for 1-2 hours, and then cooled to 30-50℃; sulfonic acid compounds, hydroxamic acid compounds, and ether compounds are added and stirred, and cooled to room temperature to obtain a brownish-brown uniform paste, which is then diluted with water to a concentration of 40%-50%.

[0031] The mass concentration of potassium hydroxide aqueous solution can be 20%-40%.

[0032] S4: Perform coarse selection, sweep selection and fine selection in sequence.

[0033] The following describes the specific implementation methods of the drugs, methods, and their performance provided in this case.

[0034] All examples and comparative examples used samples from the same batch of a refractory lithium ore. Preliminary analysis showed that the Li₂O grade fluctuated between 1.1% and 1.4%. The mineral composition was mainly spodumene and petalite, with a small amount of lepidolite; the gangue consisted primarily of feldspar and quartz. The flotation process consisted of one roughing, one scavenging, and one cleaning stage. All flotation reagents used in the examples and comparative examples were expressed in parts by weight.

[0035] Example 1 Preparation of flotation reagents: Take 40 parts of industrial oleic acid, 12 parts of sulfated vegetable oleic acid, 22 parts of sodium dodecyl sulfonate (SDS), 5 parts of salicylic acid hydroxamic acid, 5 parts of fatty alcohol polyoxyethylene ether (AEO-9), 12 parts of epoxidized soybean oleate methyl ester, and 20 parts of potassium hydroxide.

[0036] Oleic acid, sulfated oleic acid, and epoxidized soybean oleate were heated to 65°C and mixed thoroughly. A pre-prepared 30% potassium hydroxide aqueous solution was slowly added, and the mixture was stirred at 80°C for 1.5 hours. The mixture was then cooled to 40°C, and sodium dodecyl sulfonate, salicylic acid, and AEO-9 were added. The mixture was stirred at a constant speed for 30 minutes. After cooling to room temperature, a uniform brown paste was obtained, which was diluted with water to a 50% concentration for later use.

[0037] Flotation test: Take 1 kg of raw ore sample (ground to -0.074 mm, 75% of which is slurry) and prepare a 30% concentration slurry. Add pH adjusters Na₂CO₃ (800 g / t) and NaOH (200 g / t), stir for 5 minutes, and adjust the pH to 9.5. Add combined activators L-glutamate potassium (200 g / t) and glycine potassium (200 g / t), and stir for 3 minutes. Add the above flotation reagents (equivalent to 800 g / t dry weight), and stir for 2 minutes.

[0038] Flotation time: 5 minutes for roughing, 3 minutes for scavenging, and 3 minutes for cleaning, to obtain lithium concentrate and tailings.

[0039] Flotation results:

[0040] Example 2: Preparation of flotation reagents: The formula ratio was adjusted to enhance the harvesting ability: 50 parts industrial oleic acid, 15 parts sulfated vegetable oleic acid, 30 parts sodium dodecyl sulfonate, 3 parts salicylic acid hydroxamic acid, 4 parts AEO-9, 5 parts epoxidized soybean oleate methyl ester, and 30 parts potassium hydroxide. The preparation method is the same as in Example 1.

[0041] Flotation test: The flotation conditions were the same as in Example 1, but the amount of flotation reagent was reduced to 700 g / t.

[0042] Flotation results:

[0043] Analysis: Increasing the ratio of oleic acid to sodium dodecyl sulfonate further enhances the collection capacity, increasing the recovery rate to 88.45%, making it suitable for scenarios with extremely high recovery requirements.

[0044] Example 3: Preparation of flotation reagents: The formulation ratio was adjusted to enhance selectivity: 30 parts industrial oleic acid, 10 parts sulfated vegetable oleic acid, 15 parts sodium dodecyl sulfonate, 8 parts salicylic acid hydroxamic acid, 6.5 parts AEO-9, 20 parts epoxidized soybean oleate methyl ester, and 10 parts potassium hydroxide. The preparation method is the same as in Example 1.

[0045] Flotation test: The flotation conditions were the same as in Example 1, and the flotation reagent dosage was 900 g / t.

[0046] Flotation results:

[0047] Analysis: Increasing the proportion of hydroxamic acid compounds and ether compounds significantly improves selectivity, resulting in a concentrate grade as high as 6.95%, making it suitable for producing high-grade lithium concentrate.

[0048] Example 4: Flotation test: The flotation reagent prepared in Example 1 was used with the dosage reduced to 500 g / t, while all other conditions remained the same.

[0049] Flotation results:

[0050] Analysis: Even at a low dosage of 500 g / t, the reagent system of this invention can still achieve good indicators, proving its high efficiency and economy.

[0051] Example 5: Flotation test: The flotation reagents (800 g / t) and activator prepared in Example 1 were used. The pH adjuster was changed to CaO (600 g / t) and Na2CO3 (400 g / t) to adjust the pulp pH to 8.0, and the performance under weakly alkaline conditions was investigated.

[0052] Flotation results:

[0053] Analysis: The system of this invention can still maintain excellent performance under the condition of pH=8.0, which proves its wide pH adaptability.

[0054] Example 6 Pharmaceutical system: pH adjuster: Sodium carbonate (Na2CO3) 800 g / t, pH=9.0 Activator: Sodium fluoride (NaF) 50 g / t Flotation reagents: 40 parts industrial oleic acid, 12 parts sulfated vegetable oleic acid, 22 parts sodium dodecyl sulfonate, 5 parts salicylic acid hydroxamic acid, 5 parts ether compound (AEO-9), 12 parts epoxidized soybean oleate methyl ester, 25 parts KOH, with a flotation reagent dosage of 150 g / t.

[0055] Flotation results:

[0056] Comparative test of the present invention To demonstrate the beneficial effects of the technical solution of this invention, the following comparative examples were designed for verification. All experiments used the same batch of a difficult-to-process complex lithium ore sample (80% of which was -0.074mm). The flotation test procedure was as follows: grinding → pH adjustment → addition of activator → addition of flotation reagents → roughing (5 min) → three cleaning cycles → obtaining lithium concentrate and tailings. All comparative examples of this invention were conducted according to the above method.

[0057] Evaluation indicators: Li2O grade in lithium concentrate and Li2O recovery rate.

[0058] Comparative Example 1 (Traditional Oleic Acid System) Pharmaceutical preparation: pH adjuster: Sodium carbonate (Na₂CO₃) 1000 g / t, pH=9.0 Activator: Sodium fluoride (NaF) 50 g / t Flotation reagent: Industrial oleic acid (saponified with NaOH) 150 g / t Flotation results:

[0059] Results analysis: Traditional oleic acid flotation reagents have poor selectivity, and a large number of gangue minerals (especially iron and calcium-containing minerals) are floated up together, resulting in low concentrate grade and low recovery rate, making it difficult to utilize this resource economically and effectively.

[0060] Comparative Example 2 (Single Novel Sulfonic Acid Compound System) Pharmaceutical system: pH adjuster: Sodium carbonate (Na2CO3) 800 g / t, pH=9.0 Activator: Sodium fluoride (NaF) 50 g / t Flotation reagent: Sodium dodecyl sulfonate 150 g / t (i.e., the sulfonic acid compound used alone in Example 1). Flotation results:

[0061] Results analysis: Although single sulfonate flotation reagents have strong collecting ability and high yield, their selectivity is extremely poor, the concentrate grade is greatly reduced to 4.05%, the enrichment ratio is low, and qualified concentrate cannot be obtained.

[0062] Comparative Example 3 Pharmaceutical system: pH adjuster: Sodium carbonate (Na2CO3) 800 g / t, pH=9.0 Activator: Sodium fluoride (NaF) 50 g / t Flotation reagents: 45 parts industrial oleic acid, 12 parts sulfated vegetable oleic acid, 25 parts sodium dodecyl sulfonate, 15 parts epoxidized soybean oleate methyl ester and 20 parts KOH, dosage 150 g / t.

[0063] That is, no hydroxamic acid compounds or ether compounds are added.

[0064] Flotation results:

[0065] Results Analysis: The selectivity of the reagents decreased significantly after the selective chelating activation effect of hydroxamic acid compounds and the slime-dispersing effect of ether compounds were omitted. Compared with the complete formulation, both concentrate grade and recovery rate declined significantly, demonstrating a crucial synergistic effect among the components, rather than a simple additive effect. Overall Comparative Conclusions

[0066] Results Analysis: The reagent system of this invention exhibits excellent flotation performance. While ensuring high recovery, it achieves extremely high concentrate grade. The Li₂O content in the tailings decreased to 0.12%, indicating very low lithium loss. This fully demonstrates that the synergistic effect produced by the compounding of various components in this invention is far superior to any single component or formulation lacking key components, solving the technical problem of "difficulty in simultaneously achieving high recovery and high grade" in the flotation of refractory lithium ores.

[0067] This flotation reagent system exhibits a significant synergistic effect: a remarkable synergistic effect occurs among the components. Industrial oleic acid provides basic collecting properties, modified oleic acid enhances surface activity, sulfonic acid compounds improve selectivity, hydroxamic acid compounds enhance foam stability, ether compounds improve dispersibility, esterified vegetable oil enhances low-temperature adaptability, and potassium hydroxide provides appropriate saponification.

[0068] 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 flotation reagent, characterized in that: The composition by weight is as follows: unmodified oleic acid: 30-50 parts; modified oleic acid: 10-15 parts; sulfonic acid compounds: 15-30 parts; hydroxamic acid compounds: 3-8 parts; ether compounds: 4-6.5 parts; esterified vegetable oil: 5-20 parts; and potassium hydroxide: 10-30 parts.

2. The flotation reagent according to claim 1, characterized in that: The modified oleic acid includes one or more of sulfated oleic acid, sulfonated oleic acid, and esterified oleic acid; the esterified vegetable oil is selected from one or more of epoxidized soybean oleate methyl ester, epoxidized linseed oleate methyl ester, and phosphated castor oil ester.

3. The flotation reagent according to claim 1, characterized in that: The sulfonic acid compounds include at least one of sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, sulfonated kerosene, and sodium petroleum sulfonate; Or, the hydroxamic acid compounds include at least one of benzohydroxyxamic acid, salicylic acid, C5-9 hydroxamic acid, and their sodium or potassium salts.

4. A flotation method, characterized in that: The lithium ore to be processed is floated using the flotation reagents described in any one of claims 1 to 3.

5. The flotation method according to claim 4, characterized in that: The method includes the following steps: S1: Prepare lithium ore slurry from the lithium ore to be selected; S2: Adjust the pH of the slurry to 7.5-10; S3: Add flotation reagent; S4: Perform coarse selection, sweep selection and fine selection in sequence.

6. The flotation method according to claim 5, characterized in that: The concentration of the slurry is 20%-40%.

7. The flotation method according to claim 5, characterized in that: In step S2, the pH of the pulp is adjusted using a pH adjuster, which includes alkali metal carbonates and / or alkali metal hydroxides. The alkali metal carbonates are selected from one or more of potassium carbonate, sodium carbonate, and rubidium carbonate, and the alkali metal hydroxides are selected from one or more of potassium hydroxide and sodium hydroxide.

8. The flotation method according to claim 5, characterized in that: In step S3, the method further includes adding an activator, which includes sodium fluoride or an amino acid derivative, wherein the amino acid derivative is selected from one or more of monosodium glutamate, potassium glutamate, potassium glycinate, and copper glycinate.

9. The flotation method according to claim 8, characterized in that: The dosage of this activator is 50-600g per ton.

10. The flotation method according to claim 5, characterized in that: In step S3, the method includes: heating unmodified oleic acid, modified oleic acid, and esterified vegetable oil to 60-70°C and mixing them uniformly; then adding a pre-prepared aqueous solution of potassium hydroxide to the mixture; stirring at 70-90°C for 1-2 hours, then cooling to 30-50°C; then adding sulfonic acid compounds, hydroxamic acid compounds, and ether compounds, stirring, cooling to room temperature, and diluting with water to a concentration of 40%-50%.

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