A high-efficiency collector for fine-grained lithium-containing mica flotation, a preparation method and application thereof

Abstract

The application discloses a kind of microfine lithium-containing mica high-efficiency collector and its preparation method and application, and high-efficiency collector ZB-401 includes the following mass percentage of raw materials: sulfonic acid collector 60-80%, amine collector 20-40%; sulfonic acid collector and amine collector are mixed to obtain mixed reagent, mixed reagent is configured into reagent solution using 40-60 DEG C water, then add hydrochloric acid to improve its solubility, finally heated and stirred to completely dissolved, obtain high-efficiency collector ZB-401. The collector ZB-401 obtained by the method is applied to flotation process, can realize the high-efficiency recovery of microfine lithium-containing mica with particle size less than 45 μm, and the process flow is simple and efficient, the selection index is excellent, and has good application prospect.

Description

Technical Field

[0001] This invention relates to the field of flotation technology for fine-particle lithium-containing mica, and specifically to a flotation collector for fine-particle lithium-containing mica, its preparation method, and its application. Background Technology

[0002] Lepidolite is an important source of lithium metal in my country. Yichun, Jiangxi Province, is a major lepidolite production base in my country. Due to the severe impact of slime on the flotation performance of conventional lepidolite flotation reagents, most lepidolite beneficiation plants in this region use a "desliming-flotation" process to recover coarse-grained (particle size greater than 45 μm) lepidolite minerals. However, fine-grained lepidolite particles smaller than 45 μm are generally discarded along with the desliming product, resulting in significant resource waste; the lithium metal loss rate in the slime alone is as high as 30%. Therefore, to improve the utilization rate of lepidolite resources, it is necessary to develop highly efficient flotation reagents, especially high-performance collectors, for fine-grained lepidolite minerals.

[0003] To better recover lithium-containing mica resources, previous scholars have conducted extensive research. For example, the invention patent filed on October 10, 2022, with application number 202211235355.X, discloses a beneficiation method for lithium extraction from lithium-containing kaolin ore using a magnetic-flotation combined process. This method involves a lithium mica collector, ZY-07, which is obtained by mixing cotton oil, cocoamine, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and styrenephosphonic acid in a mass ratio of 2:3:(1-2):1. This collector can recover lithium-containing minerals from lithium-containing kaolin ore with a fineness of -0.074 mm (35%-50%) and a raw ore Li₂O content of 0.3%-0.5%. However, the flotation performance of collector ZY-07 for fine lithium-containing mica particles smaller than 45 μm remains to be verified.

[0004] For example, the invention patent with application date of July 5, 2022, and application number 202210783096.8, discloses a flotation-magnetic combined beneficiation method for recovering fine-grained lepidolite from tailings. This method requires a combination of flotation column and centrifugal high-gradient magnetic separation to recover lepidolite from tailings. The collector used in flotation is a combination of oxidized paraffin soap and dodecylamine. This method has a relatively complex process flow, requiring flotation and magnetic separation to work together to recover fine-grained lepidolite, resulting in relatively high costs.

[0005] Therefore, developing efficient collectors for fine-grained lithium mica minerals (lithium mica and lepidolite) with a particle size of less than 45 micrometers to achieve efficient recovery of lithium mica minerals from tailings products is of great significance for improving the utilization efficiency of my country's precious lithium mica resources and is also very beneficial to improving the economic benefits of lithium mica beneficiation plants in Yichun, Jiangxi Province. Summary of the Invention

[0006] This invention aims to overcome the shortcomings of existing technologies and proposes a highly efficient collector for the flotation of fine-grained lithium-containing mica, its preparation method, and its application. The collector ZB-401 obtained by this method can be applied to the flotation process to achieve efficient recovery of fine-grained lithium-containing mica with a particle size of less than 45 μm. Moreover, the process is simple and efficient, with excellent separation indicators and good application prospects.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a high-efficiency collector for the flotation of fine-particle lithium-containing mica, wherein the high-efficiency collector ZB-401 comprises the following raw materials in mass percentage: 60%-80% sulfonic acid collector and 20%-40% amine collector.

[0008] Furthermore, the sulfonic acid collector is one or both of sodium dodecyl sulfonate and sodium petroleum sulfonate.

[0009] Furthermore, the amine collector is one or both of dodecylamine and oleylamine.

[0010] Furthermore, the mass percentage of sulfonic acid collectors is 60-76%, and the mass percentage of amine collectors is 24-40%.

[0011] A method for preparing a highly efficient collector for the flotation of fine-particle lithium-containing mica includes the following steps:

[0012] (1) Mix sulfonic acid collectors and amine collectors to obtain a mixed agent;

[0013] (2) Prepare a 20% (w / w) solution of the mixed agent using water at 40-60℃, and then add 1-2% (w / w) of hydrochloric acid to improve its solubility;

[0014] (3) Heat and stir the reagent solution after adding hydrochloric acid to prepare a milky white solution. After the mixed reagent is completely dissolved, the high-efficiency collector ZB-401 is obtained.

[0015] Furthermore, in step (3), water bath heating is used, the heating temperature is 60-80℃, the stirring speed is 500-800r / min, and the stirring time is 15-30min.

[0016] The application of a highly efficient collector for the flotation of fine-particle lithium-containing mica includes the following steps:

[0017] (1) The fine-grained lithium-containing mica slime is classified, with the +0.010mm particle size product used as flotation feed and the -0.010mm particle size product used as the final slime product.

[0018] (2) The 0.010mm particle size product is subjected to a first stage of roughing to obtain roughing concentrate and roughing tailings. The roughing concentrate is subjected to multiple stages of fine cleaning to obtain the final concentrate. The roughing tailings are subjected to a first stage of scavenging to obtain scavenging concentrate and tailings. The scavenging concentrate is returned to the first stage of roughing. Inhibitors and collector ZB-401 are added to the first stage of roughing and the first stage of scavenging.

[0019] Further, the depressants are sodium hexametaphosphate and water glass; in the first-stage roughing, the dosage is 200 g / t of sodium hexametaphosphate, 1000 g / t of water glass, and 100-200 g / t of collector ZB-401, with a flotation time of 2 min; in the first-stage scavenging, the dosage is 50 g / t of sodium hexametaphosphate, 250 g / t of water glass, and 50-100 g / t of collector ZB-401, with a flotation time of 1 min. The dosage of collector ZB-401 in the first-stage roughing can be 100 g / t, 125 g / t, 150 g / t, 175 g / t, 200 g / t, etc., while the dosage of collector ZB-401 in the first-stage scavenging can be 50 g / t, 60 g / t, 70 g / t, 75 g / t, 85 g / t, 90 g / t, 100 g / t, etc.

[0020] Furthermore, a pH adjuster, namely NaOH, was added during the initial coarse selection process at a dosage of 200 g / t.

[0021] Furthermore, the particle size of the fine-grained lithium-containing mica mud is less than 45 micrometers.

[0022] The beneficial effects of this invention are as follows:

[0023] This invention utilizes the synergistic effect of different collectors to efficiently recover fine-grained lithium mica minerals such as lepidolite and lithium-bearing mica with a particle size of less than 45 micrometers. Compared with the direct addition of sulfonic acid and amine collectors, the high-efficiency collector ZB-401 prepared by this invention can increase the concentrate Li2O grade by approximately 0.2% and the Li2O recovery rate by more than 10%. This invention uses common flotation reagents to prepare the high-efficiency collector ZB-401, which has advantages such as simple method, readily available and inexpensive raw materials, low cost, and excellent flotation indicators. It can achieve efficient recovery of fine-grained lithium mica resources from mineral processing plant waste slime (with a particle size of -0.030mm or more accounting for over 80%), improving the utilization efficiency of lithium mica resources. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0025] Figure 1 This is a flotation process flow diagram of the application of collector ZB-401 in a specific embodiment of the present invention. Detailed Implementation

[0026] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1

[0028] The sulfonic acid collectors comprise 66% by mass, of which sodium dodecyl sulfonate comprises 33% and sodium petroleum sulfonate comprises 33% by mass; the amine collectors comprise 34% by mass, of which dodecylamine comprises 17% and oleylamine comprises 17% by mass.

[0029] The preparation method is as follows: Sodium dodecyl sulfonate, sodium petroleum sulfonate, dodecylamine, and oleylamine are mixed according to a predetermined mass percentage; the mixed reagent is prepared into a 20% reagent solution using tap water at 50 degrees Celsius; 1.5% hydrochloric acid (using 35wt.% hydrochloric acid) is added to the reagent solution to improve its solubility; the mixed reagent after adding hydrochloric acid is heated and stirred in a water bath at 60 degrees Celsius, with a stirring intensity of 800 r / min and a stirring time of 30 min. After complete dissolution, the high-efficiency collector ZB-401 is obtained.

[0030] Example 2

[0031] The sulfonic acid collector has a mass percentage of 76%, of which sodium dodecyl sulfonate accounts for 76%; the amine collector has a mass percentage of 24%, of which dodecylamine accounts for 24%.

[0032] The preparation method is as follows: Sodium dodecyl sulfonate and dodecylamine are mixed according to a predetermined mass percentage; the mixed reagent is prepared into a 20% reagent solution using tap water at 60 degrees Celsius; 2% hydrochloric acid (using 35wt.% hydrochloric acid) is added to the reagent solution to improve its solubility; the mixed reagent after adding hydrochloric acid is heated and stirred in a water bath at 80 degrees Celsius, with a stirring intensity of 600 r / min and a stirring time of 20 min. After complete dissolution, the high-efficiency collector ZB-401 is obtained.

[0033] Example 3

[0034] The sulfonic acid collector has a mass percentage of 60%, of which sodium petroleum sulfonate accounts for 60%; the amine collector has a mass percentage of 40%, of which dodecylamine accounts for 40%.

[0035] The preparation method is as follows: sodium petroleum sulfonate and dodecylamine are mixed according to a predetermined mass percentage; the mixed reagent is prepared into a 20% reagent solution using tap water at 50 degrees Celsius; 1.5% hydrochloric acid (using 35wt.% hydrochloric acid) is added to the reagent solution to improve its solubility; the mixed reagent after adding hydrochloric acid is heated and stirred in a water bath at 60 degrees Celsius, with a stirring intensity of 800 r / min and a stirring time of 20 min. After complete dissolution, the high-efficiency collector ZB-401 is obtained.

[0036] Example 4

[0037] This study uses tailings (fine-grained lithium mica mud) from a lithium mica beneficiation plant in Yuanzhou District, Yichun City, Jiangxi Province as the application object. The tailings have a fineness of -0.030 mm (83.56%) and a Li₂O content of 0.20%. This example is a comparative experiment on the effect of collector ZB-401. The experimental procedure strictly followed... Figure 1 The process shown includes the following steps:

[0038] 1) Weigh 600g of fine tailings product for classification. The +0.010mm particle size product is used as flotation feed, and the -0.010mm particle size product is used as the final slime product.

[0039] 2) Prepare a 20% concentration slurry from the +0.010mm particle size product. Transfer the slurry to an XFD 1.5L flotation cell for roughing. Add pH adjuster, inhibitor, and collector sequentially to the roughing cell. After stirring for 3 minutes each, start aeration flotation to obtain roughing concentrate and roughing tailings. Transfer the roughing concentrate to a 750ml flotation cell for cleaning. Perform scavenging once on the roughing tailings. Return the scavenged concentrate (mid-minerals 4) to the roughing cell. The scavenged tailings are the final tailings. Perform cleaning three times on the roughing concentrate in the 750ml flotation cell. Return mid-minerals 1 to the roughing cell, mid-minerals 2 to the cleaning cell 1, and mid-minerals 3 to the cleaning cell 2. The concentrate obtained from cleaning cell 3 is the final concentrate.

[0040] The reagent conditions for this embodiment are as follows: The collector ZB-401 prepared in Example 1 is used. Specifically, the roughing reagent regimen is: NaOH 200 g / t, sodium hexametaphosphate 200 g / t, water glass 1000 g / t, collector ZB-401 prepared in Example 1 150 g / t, flotation time 2 min; the scavenging reagent regimen is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, collector ZB-401 prepared in Example 1 75 g / t, flotation time 1 min; the cleaning reagent regimen 1 is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, flotation time 1.5 min; the cleaning reagent regimen 2 is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, flotation time 1.5 min; the cleaning reagent regimen 3 is: sodium hexametaphosphate 25 g / t, water glass 125 g / t, flotation time 1 min.

[0041] As a comparison condition 1: Lithium mica using conventional collector dodecylamine. Specifically, the roughing reagent regimen was: NaOH 200 g / t, sodium hexametaphosphate 200 g / t, water glass 1000 g / t, dodecylamine collector 150 g / t, flotation time 2 min; the scavenging reagent regimen was: sodium hexametaphosphate 50 g / t, water glass 250 g / t, dodecylamine collector 75 g / t, flotation time 1 min; the cleaning reagent regimen 1 was: sodium hexametaphosphate 50 g / t, water glass 250 g / t, flotation time 1.5 min; the cleaning reagent regimen 2 was: sodium hexametaphosphate 50 g / t, water glass 250 g / t, flotation time 1.5 min; the cleaning reagent regimen 3 was: sodium hexametaphosphate 25 g / t, water glass 125 g / t, flotation time 1 min.

[0042] Table 1 Comparison of flotation effects of collector ZB-401 and dodecylamine

[0043]

[0044]

[0045] Analysis of Table 1 shows that, compared with the conventional collector dodecylamine, the collector ZB-401 prepared in Example 1 increased the Li2O grade of the concentrate by 0.30% and the Li2O recovery rate by 28.78%. This indicates that, compared with the conventional collector dodecylamine, the collector ZB-401 prepared in Example 1 has better selective collection ability for fine-grained lithium-containing mica.

[0046] Example 5

[0047] Tailings from a lithium mica beneficiation plant in Gao'an City, Yichun City, Jiangxi Province, were used as the application object. The tailings had a fineness of -0.030 mm (86.95%) and a Li₂O content of 0.30%. This example is a comparative experiment on the effect of collector ZB-401. The experimental procedure strictly followed... Figure 1 The process shown is carried out, and the specific flotation process is the same as in Example 4.

[0048] The reagent conditions for this embodiment are as follows: The collector ZB-401 prepared in Example 2 is used. Specifically, the roughing reagent regimen is: NaOH 200 g / t, sodium hexametaphosphate 200 g / t, water glass 1000 g / t, collector ZB-401 prepared in Example 2 150 g / t, flotation time 2 min; the scavenging reagent regimen is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, collector ZB-401 prepared in Example 2 75 g / t, flotation time 1 min; the cleaning reagent regimen 1 is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, flotation time 1.5 min; the cleaning reagent regimen 2 is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, flotation time 1.5 min; the cleaning reagent regimen 3 is: sodium hexametaphosphate 25 g / t, water glass 125 g / t, flotation time 1 min.

[0049] As a comparative condition 2: the lithium mica collector is sodium dodecyl sulfonate and dodecylamine, which are added directly according to the conventional mineral processing reagent usage method, and are not prepared using the preparation method of this application. Specifically, the reagent regime for roughing is: NaOH 200g / t, sodium hexametaphosphate 200g / t, water glass 1000g / t, sodium dodecyl sulfate collector 114g / t, dodecylamine 36g / t, with a flotation time of 2 min; the reagent regime for scavenging is: sodium hexametaphosphate 50g / t, water glass 250g / t, sodium dodecyl sulfate collector 57g / t, dodecylamine 18g / t, with a flotation time of 1 min; the reagent regime for cleaning 1 is: sodium hexametaphosphate 50g / t, water glass 250g / t, with a flotation time of 1.5 min; the reagent regime for cleaning 2 is: sodium hexametaphosphate 50g / t, water glass 250g / t, with a flotation time of 1.5 min; and the reagent regime for cleaning 3 is: sodium hexametaphosphate 25g / t, water glass 125g / t, with a flotation time of 1 min.

[0050] Table 2 Comparison of flotation effects of collector ZB-401 with sodium dodecyl sulfonate and dodecylamine by direct addition.

[0051]

[0052] Analysis of Table 2 shows that, compared with the direct addition of collectors sodium dodecyl sulfonate and dodecylamine, the collector ZB-401 prepared in Example 2 increased the Li2O grade of the concentrate by 0.24% and the Li2O recovery rate by 17.61%. This indicates that, compared with the direct addition of collectors sodium dodecyl sulfonate and dodecylamine, collector ZB-401, prepared by the method of this invention, can better exert the synergistic collecting effect of the two collectors and has a stronger selective collecting effect on fine-grained lithium-containing mica.

[0053] Example 6

[0054] Tailings from a lithium mica beneficiation plant in Gao'an City, Yichun City, Jiangxi Province, were used as the application object. The tailings had a fineness of -0.030 mm (86.95%) and a Li₂O content of 0.30%. This example is a comparative experiment on the effect of collector ZB-401. The experimental procedure strictly followed... Figure 1 The process shown is carried out, and the specific flotation process is the same as in Example 4.

[0055] The reagent conditions for this embodiment are as follows: The collector ZB-401 prepared in Example 3 is used. Specifically, the roughing reagent regimen is: NaOH 200 g / t, sodium hexametaphosphate 200 g / t, water glass 1000 g / t, collector ZB-401 prepared in Example 3 150 g / t, flotation time 2 min; the scavenging reagent regimen is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, collector ZB-401 prepared in Example 3 75 g / t, flotation time 1 min; the cleaning reagent regimen 1 is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, flotation time 1.5 min; the cleaning reagent regimen 2 is: sodium hexametaphosphate 50 g / t, water glass 250 g / t, flotation time 1.5 min; the cleaning reagent regimen 3 is: sodium hexametaphosphate 25 g / t, water glass 125 g / t, flotation time 1 min.

[0056] As a comparative condition 3: the lithium mica collector is sodium petroleum sulfonate and dodecylamine, which are added directly according to the conventional mineral processing reagent usage method, and are not prepared using the method of this application. Specifically, the reagent regime for roughing is 200 g / t NaOH, 200 g / t sodium hexametaphosphate, 1000 g / t water glass, 90 g / t sodium petroleum sulfonate collector, and 60 g / t dodecylamine, with a flotation time of 2 min; the reagent regime for scavenging is 50 g / t sodium hexametaphosphate, 250 g / t water glass, 45 g / t sodium petroleum sulfonate collector, and 30 g / t dodecylamine, with a flotation time of 1 min; the reagent regime for cleaning 1 is 50 g / t sodium hexametaphosphate and 250 g / t water glass, with a flotation time of 1.5 min; the reagent regime for cleaning 2 is 50 g / t sodium hexametaphosphate and 250 g / t water glass, with a flotation time of 1.5 min; and the reagent regime for cleaning 3 is 25 g / t sodium hexametaphosphate and 125 g / t water glass, with a flotation time of 1 min.

[0057] Table 3 Comparison of flotation effects of collector ZB-401, sodium petroleum sulfonate, and dodecylamine when directly added.

[0058]

[0059] Analysis of Table 3 shows that, compared with the direct addition of collectors sodium petroleum sulfonate and dodecylamine, the collector ZB-401 prepared in Example 3 increased the Li2O grade of the concentrate by 0.19% and the Li2O recovery rate by 11.85%. This indicates that, compared with the direct addition of collectors sodium petroleum sulfonate and dodecylamine, collector ZB-401, prepared by the method of this invention, can better exert the synergistic collecting effect of the two collectors and has a stronger selective collecting effect on fine-particle lithium-containing mica.

[0060] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A highly efficient collector for the flotation of fine-particle lithium-containing mica, characterized in that: The high-efficiency collector ZB-401 comprises the following raw materials by mass percentage: 60%-80% sulfonic acid collector and 20%-40% amine collector; The sulfonic acid collector is one or both of sodium dodecyl sulfonate and sodium petroleum sulfonate; The amine collector is one or both of dodecylamine and oleylamine; The preparation method of this highly efficient collector for lithium-containing mica flotation includes the following steps: (1) Mix sulfonic acid collectors and amine collectors to obtain a mixed agent; (2) Prepare a 20% (w / w) solution of the mixed reagents using water at 40-60℃, and then add 1-2% (w / w) hydrochloric acid. (3) Heat and stir the reagent solution after adding hydrochloric acid to prepare a milky white solution. After the mixed reagent is completely dissolved, the high-efficiency collector ZB-401 is obtained. Use water bath heating, the heating temperature is 60-80℃, the stirring speed is 500-800r / min, and the stirring time is 15-30min.

2. The application of the high-efficiency collector for the flotation of fine-particle lithium-containing mica as described in claim 1, characterized in that, The application method includes the following steps: 1) The fine-grained lithium-containing mica slime is classified, with the +0.010mm particle size product used as flotation feed and the -0.010mm particle size product used as the final slime product; 2) The +0.010mm particle size product undergoes a first-stage roughing process to obtain roughing concentrate and roughing tailings. The roughing concentrate undergoes multiple stages of cleaning to obtain the final concentrate. The roughing tailings undergo a first-stage scavenging process to obtain scavenging concentrate and tailings. The scavenging concentrate is returned to the first-stage roughing process. Inhibitors and collector ZB-401 are added to the first-stage roughing process and the first-stage scavenging process.

3. The application according to claim 2, characterized in that, The depressants are sodium hexametaphosphate and water glass; in the first roughing stage, the flotation concentrations are: sodium hexametaphosphate 200 g / t, water glass 1000 g / t, collector ZB-401 100-200 g / t, and flotation time 2 min; in the first scavenging stage, the concentrations are: sodium hexametaphosphate 50 g / t, water glass 250 g / t, collector ZB-401 50-100 g / t, and flotation time 1 min.

4. The application according to claim 2 or 3, characterized in that, A pH adjuster, namely NaOH, was added during the initial screening process at a dosage of 200g / t.

5. The application according to claim 2, characterized in that, The particle size of the fine-grained lithium-containing mica mud is less than 45 micrometers.

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