A collector and its use, collector solution

Abstract

The application provides a kind of collector and its application, collector solution, belongs to lithium mica flotation technical field.The collector provided by the application includes octadecylamine and polyoxyethylene ether;The mass ratio of octadecylamine and polyoxyethylene ether is (5~15):1.The collector of the application is compounded by octadecylamine and polyoxyethylene ether, polyoxyethylene ether has hydrophilic ether oxygen chain and hydrophobic carbon hydrogen chain segment, can simultaneously play the functions of auxiliary foaming and dispersion solubilization, so as to improve the flotation separation effect of collector on lithium mica;By limiting the mass ratio of octadecylamine and polyoxyethylene ether, the flotation separation effect of collector on lithium mica can be further improved.The results of examples show that the Li2O grade of lithium mica rough concentrate obtained by using the collector provided by the application for one roughing is 1.39%, the recovery rate is 79.10%, and the separation efficiency is 74.16%.

Description

Technical Field

[0001] This invention belongs to the field of lithium mica flotation technology, specifically relating to a collector and its application, and a collector solution. Background Technology

[0002] Lepidolite is an important mineral raw material for extracting lithium and its compounds. With the rapid development of the new energy industry, global lithium demand continues to grow, and the efficient recovery of lithium from low-grade lepidolite ore has become a research hotspot in the field of mineral processing. Flotation is the main industrial method for enriching lepidolite, and cationic collectors are widely used due to their electrostatic adsorption on negatively charged sites in layered silicate mineral layers.

[0003] Octadecylamine (ODA) is the most commonly used collector in lepidolite flotation, exhibiting excellent selective collection ability for lepidolite. However, ODA suffers from poor water solubility, poor dispersibility in slurry, and a tendency to solidify and precipitate at low temperatures, and it also has poor foaming properties when used alone. These defects result in unsatisfactory flotation performance when ODA is used alone. For example, taking lepidolite ore with a Li₂O grade of 0.24% as an example, using 300 g / t of ODA alone results in a Li₂O grade of only 0.75% in the lepidolite concentrate, a recovery rate of 65.26%, and a separation efficiency of less than 50%. Therefore, how to improve the flotation and separation effect of lepidolite has become a pressing technical challenge in this field. Summary of the Invention

[0004] The purpose of this invention is to provide a collector and its application, as well as a collector solution. The collector provided by this invention can improve the flotation and separation efficiency of lepidolite when used in the flotation of lepidolite.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a collector comprising octadecylamine and polyoxyethylene ether; The mass ratio of octadecylamine to polyoxyethylene ether is (5~15):1.

[0006] Preferably, the polyoxyethylene ether includes one or more of fatty alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, and fatty amine polyoxyethylene ether.

[0007] Preferably, when the polyoxyethylene ether is a fatty alcohol polyoxyethylene ether, the mass ratio of the octadecylamine to the polyoxyethylene ether is (5~8):1.

[0008] Preferably, when the polyoxyethylene ether is octylphenol polyoxyethylene ether, the mass ratio of octadecylamine to polyoxyethylene ether is (5~8):1.

[0009] Preferably, when the polyoxyethylene ether is a fatty amine polyoxyethylene ether, the mass ratio of the octadecylamine to the polyoxyethylene ether is (10~13):1.

[0010] The present invention also provides a collector solution, which is obtained by mixing the collector, acid and water described in the above technical solution.

[0011] Preferably, the mass concentration of the acid is 36-38%, and the mass ratio of the acid to octadecylamine is (2-6):1.

[0012] The present invention also provides the application of the collector described in the above technical solution in the flotation of lepidolite.

[0013] Preferably, the amount of collector used is 200~400g / t, based on the mass of lepidolite ore during lepidolite flotation.

[0014] Preferably, the application includes: Lithium mica ore is slurry prepared to obtain lithium mica slurry; The collector, acid, and water are mixed to obtain a collector solution; The collector solution and lepidolite slurry are mixed and then subjected to flotation.

[0015] This invention provides a collector comprising octadecylamine and polyoxyethylene ether; the mass ratio of octadecylamine to polyoxyethylene ether is (5~15):1. The collector of this invention uses a compound of octadecylamine and polyoxyethylene ether. Polyoxyethylene ether possesses both hydrophilic ether oxygen chains and hydrophobic hydrocarbon segments, simultaneously functioning as an auxiliary foaming and dispersing solubilizer, thereby improving the flotation separation effect of the collector on lepidolite. By limiting the mass ratio of octadecylamine to polyoxyethylene ether, the flotation separation effect of the collector on lepidolite can be further improved. The results of the embodiments show that the lepidolite rough concentrate obtained by a single roughing process using the collector provided by this invention has a Li2O grade of 1.39%, a recovery rate of 79.10%, and a separation efficiency of 74.16%. Detailed Implementation

[0016] The present invention provides a collector comprising octadecylamine (ODA) and polyoxyethylene ether; The mass ratio of octadecylamine to polyoxyethylene ether is (5~15):1.

[0017] This invention does not impose any special restrictions on the source of the raw materials; commercially available products familiar to those skilled in the art can be used.

[0018] In this invention, the polyoxyethylene ether preferably includes one or more of fatty alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, and fatty amine polyoxyethylene ether. This invention uses polyoxyethylene ether as a nonionic surfactant, which possesses both hydrophilic ether oxygen chains and hydrophobic hydrocarbon segments, enabling it to simultaneously perform auxiliary foaming and dispersing / solubilizing functions, thereby improving the flotation and separation effect of the collector on lepidolite.

[0019] In one embodiment, the fatty alcohol polyoxyethylene ether can be AEO-9. In this invention, when the polyoxyethylene ether is a fatty alcohol polyoxyethylene ether, the preferred mass ratio of the octadecylamine to the polyoxyethylene ether is (5~8):1. In another embodiment, when the polyoxyethylene ether is a fatty alcohol polyoxyethylene ether, the mass ratio of the octadecylamine to the polyoxyethylene ether can be 6:1 or 7:1.

[0020] In one embodiment, the octylphenol polyoxyethylene ether can be OP-10. In this invention, when the polyoxyethylene ether is octylphenol polyoxyethylene ether, the preferred mass ratio of the octadecylamine to the polyoxyethylene ether is (5~8):1. In another embodiment, when the polyoxyethylene ether is polyoxyethylene ether, the mass ratio of the octadecylamine to the polyoxyethylene ether can be 6:1 or 7:1.

[0021] In one embodiment, the fatty amine polyoxyethylene ether can be AC1210. In this invention, when the polyoxyethylene ether is a fatty amine polyoxyethylene ether, the preferred mass ratio of octadecylamine to polyoxyethylene ether is (10~13):1. In another embodiment, when the polyoxyethylene ether is a polyoxyethylene ether, the mass ratio of octadecylamine to polyoxyethylene ether can be 11:1 or 12:1.

[0022] The collector of the present invention is a compound of octadecylamine and polyoxyethylene ether. Polyoxyethylene ether has both hydrophilic ether oxygen chain and hydrophobic hydrocarbon chain segment, which can simultaneously play the functions of assisting foaming and dispersing solubilization, thereby improving the flotation separation effect of the collector on lepidolite. By limiting the mass ratio of octadecylamine and polyoxyethylene ether, the flotation separation effect of the collector on lepidolite can be further improved.

[0023] The present invention also provides a collector solution, which is obtained by mixing the collector, acid and water described in the above technical solution.

[0024] In this invention, the preferred mass concentration of the acid is 36-38%; the preferred mass ratio of the acid to octadecylamine is (2-6):1. As one embodiment, the mass concentration of the acid can be 37%; the acid can be hydrochloric acid; and the mass ratio of the acid to octadecylamine can be 3:1, 4:1, or 5:1. This invention can further improve water solubility and harvesting performance by controlling the mass ratio of the acid to octadecylamine.

[0025] The present invention does not have a special limitation on the amount of water used; it can be selected according to the mass concentration of the required collector solution.

[0026] In this invention, the preferred mixing temperature for the collector, acid, and water is 40-80°C. As one embodiment, the mixing temperature for the collector, acid, and water can be 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, or 75°C. This invention does not impose a specific limitation on the mixing time, as long as a homogeneous solution is obtained.

[0027] In this invention, the preferred mixture of the collector, acid, and water is: Mix octadecylamine and polyoxyethylene ether, then add acid and water; Alternatively, octadecylamine, acid, and water can be mixed to obtain an ammonium salt solution; polyoxyethylene ether and water can be mixed to obtain a polyoxyethylene ether solution; and then the ammonium salt solution and the polyoxyethylene ether solution can be mixed.

[0028] In this invention, the mass concentration of octadecylamine in the ammonium salt solution and the mass concentration of the polyoxyethylene ether solution are preferably the same.

[0029] In this invention, the method of mixing the collector solution and the lepidolite slurry within 3 minutes after the ammonium salt solution and the polyoxyethylene ether solution are mixed is called mixing and adding immediately, and the method of mixing the collector solution and the lepidolite slurry after more than 3 minutes, preferably more than 10 minutes, is called the pre-mixing method; the first mixing method mentioned above is also the pre-mixing method.

[0030] In this invention, the total mass concentration of octadecylamine and polyoxyethylene ether in the collector solution is preferably 1-10%. As one embodiment, the total mass concentration of octadecylamine and polyoxyethylene ether in the collector solution can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%.

[0031] This invention also provides the application of the collector described in the above technical solution in the flotation of lepidolite.

[0032] The collector provided by this invention is applicable to any lithium mica ore.

[0033] In this invention, based on the mass of lepidolite ore during lepidolite flotation, the preferred dosage of the collector is 200-400 g / t. As one embodiment, based on the mass of lepidolite ore during lepidolite flotation, the dosage of the collector can be 250 g / t, 300 g / t, 325 g / t, 350 g / t, or 360 g / t. Limiting the collector dosage within the above range further improves the collecting performance.

[0034] In this invention, the application preferably includes: Lithium mica ore is slurry prepared by mixing it with other materials to obtain lithium mica slurry. The collector, acid, and water are mixed to obtain a collector solution; The collector solution and lepidolite slurry are mixed and then subjected to flotation.

[0035] The present invention preferably involves adjusting the lepidolite slurry to obtain a lepidolite slurry.

[0036] In this invention, the lepidolite preferably undergoes sequential crushing and grinding before use. This invention does not impose any particular limitation on the particle size of the lepidolite; any particle size well-known to those skilled in the art can be used.

[0037] The present invention does not impose any special limitations on the slurry preparation operation. Operations familiar to those skilled in the art can be used, as long as the required slurry concentration is obtained.

[0038] In this invention, the preferred mass concentration of the lepidolite slurry is 25-40%; the preferred pH value of the lepidolite slurry is 5-9. As one embodiment, the mass concentration of the lepidolite slurry can be 30%, 35%, or 38%; the pH value of the lepidolite slurry can be 6, 7, or 8. In this invention, the pH value of the lepidolite slurry is the inherent pH value of the lepidolite ore after dispersion at the above concentrations.

[0039] In this invention, the method for preparing the collector solution is preferably the same as the method described above for preparing the collector solution, and will not be repeated here.

[0040] After obtaining the lepidolite slurry and the collector solution, the present invention preferably mixes the collector solution and the lepidolite slurry for flotation.

[0041] The present invention does not impose any particular limitation on the operation of mixing the collector solution and the lepidolite slurry; any technical solution for preparing the mixture well known to those skilled in the art can be used. As one embodiment, the mixing of the collector solution and the lepidolite slurry can be carried out under stirring conditions; the stirring time can be 2-5 minutes, or even 3 minutes.

[0042] The present invention does not impose any special limitations on the flotation operation; any flotation operation well known to those skilled in the art can be used. As one embodiment, the flotation can be aeration flotation.

[0043] The advantages of this invention over existing pharmaceuticals or processes are as follows: (1) The sorting efficiency is significantly improved. By using pre-mixed collector solution, a rough concentrate with a Li2O grade of more than 1.2% and a recovery rate of more than 78% can be obtained in the roughing stage. The sorting efficiency is more than 73%, which is more than 23% higher than that of using ODA alone (about 50%) and more than 8% higher than that of the on-site mixing method.

[0044] (2) High-efficiency separation under neutral slurry conditions. The flotation process of the present invention is carried out at the natural pH value of the slurry, without the need to add acid or alkali to adjust the pH of the slurry, which simplifies the process flow and reduces equipment corrosion and wastewater treatment pressure.

[0045] (3) Good process versatility. Pre-mixing avoids the ratio error caused by adding the two agents separately on site; after pre-mixing, the sorting efficiency of octadecylamine and polyoxyethylene ether (AEO-9, OP-10 or AC1210) tends to be consistent (73~74%), and polyoxyethylene ether with different structures can obtain similar indicators, providing a flexible agent selection space for the production site.

[0046] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0047] The flotation effect of this invention uses the Hancock-Luikon separation efficiency η as a comprehensive evaluation index, and the calculation formula is η=(ε-γ) / (1-α / β) max )×100%, where ε is the concentrate recovery rate, γ is the concentrate yield, α is the feed grade, and β is the feed grade. max This represents the theoretical highest grade for lithium-bearing minerals. Based on the properties of the research object, β max The value is 2.0%. This sorting efficiency can take into account both grade and recovery rate, avoiding the one-sided evaluation of a single indicator.

[0048] Example 1 The collector is ODA and AEO-9 in a mass ratio of 6:1.

[0049] Application Example 1 The application of Example 1 to the flotation of lithium mica was carried out as follows: Lithium mica ore (Li2O grade of about 0.24%, lithium-containing minerals are lepidolite and muscovite, with a mass ratio of about 1:2, gangue minerals are mainly albite, quartz and potassium feldspar, and the yield of the -0.074mm particle size in the flotation sample is 28.65%) was added to an XFD-1.5L flotation machine, and tap water was used to adjust the slurry to a mass concentration of 38% to obtain lepidolite slurry; ODA, AEO-9, hydrochloric acid (mass concentration of 37%, mass ratio of hydrochloric acid to ODA of 4:1) and an appropriate amount of water were stirred and mixed in a water bath at 50°C until homogeneous to obtain a collector solution with a mass concentration of 2%. The collector solution is added to the lepidolite slurry 30 minutes after preparation, stirred for 3 minutes, aerated and skimmed, and roughed once to obtain lepidolite rough concentrate; wherein, based on the mass of lepidolite ore during lepidolite flotation, the amount of collector used is 300 g / t.

[0050] In Application Example 1, the Li2O grade of the lepidolite concentrate was 1.39%, the recovery rate was 78.79%, and the separation efficiency was 74.07%.

[0051] Example 2 Based on Example 1, AEO-9 was modified to OP-10, while other conditions remained unchanged.

[0052] Application Example 2 Based on Application Example 1, the collector in Example 1 was modified to that in Example 2, while other conditions remained unchanged.

[0053] In Application Example 2, the Li2O grade of the lepidolite concentrate obtained was 1.37%, the recovery rate was 79.10%, and the separation efficiency was 74.16%.

[0054] Example 3 The collector is ODA and AC1210 in a mass ratio of 12:1.

[0055] Application Example 3 Based on Application Example 1, the collector in Example 1 was modified to that in Example 3, while other conditions remained unchanged.

[0056] In Application Example 3, the Li2O grade of the lepidolite concentrate obtained was 1.29%, the recovery rate was 79.05%, and the separation efficiency was 73.14%.

[0057] Application Example 4 The application of Example 1 to the flotation of lithium mica was carried out as follows: Lithium mica ore (Li2O grade of about 0.24%, lithium-containing minerals are lepidolite and muscovite, with a mass ratio of about 1:2, gangue minerals are mainly albite, quartz and potassium feldspar, and the yield of the -0.074mm particle size in the flotation sample is 28.65%) was added to an XFD-1.5L flotation machine, and tap water was used to adjust the slurry to a mass concentration of 38% to obtain lepidolite slurry; ODA, hydrochloric acid (mass concentration of 37%, mass ratio of hydrochloric acid to ODA of 4:1) and an appropriate amount of water were stirred and mixed in a water bath at 50°C until homogeneous to obtain an ammonium salt solution with a mass concentration of 2%. AEO-9 and water were stirred and mixed in a 50°C water bath until homogeneous to obtain a polyoxyethylene ether solution with a mass concentration of 2%. The ammonium salt solution and polyoxyethylene ether solution are added to the slurry within 3 minutes after mixing. The amount of collector used is 350 g / t, based on the mass of the lepidolite ore during lepidolite flotation, while other conditions remain unchanged.

[0058] In Application Example 4, the Li2O grade of the lepidolite concentrate was 1.02%, the recovery rate was 75.21%, and the separation efficiency was 65.27%.

[0059] Application Example 5 Based on Application Example 4, the collector in Example 1 was modified to that in Example 2, while other conditions remained unchanged.

[0060] In Application Example 5, the Li2O grade of the lepidolite concentrate was 1.08%, the recovery rate was 74.74%, and the separation efficiency was 65.46%.

[0061] Application Example 6 Based on Application Example 4, the collector in Example 1 was modified to that in Example 3. The amount of collector used was 325 g / t, with the mass of lepidolite ore used during lepidolite flotation as the benchmark, and other conditions remained unchanged.

[0062] In Application Example 6, the lepidolite concentrate had a Li2O grade of 0.84%, a recovery rate of 77.59%, and a separation efficiency of 63.56%.

[0063] Comparative Example 1 Based on Example 1, only ODA is added.

[0064] Comparative Application Example 1 Based on Application Example 1, Example 1 was modified into Comparative Example 1, with 30g / t of No. 2 oil added as a frother. The mass of lepidolite ore during lepidolite flotation was used as the benchmark, and the ODA dosage was 300g / t, with other conditions remaining unchanged.

[0065] Compared with the Li2O grade of lepidolite crude concentrate obtained in Application Example 1, the recovery rate was 65.26% and the separation efficiency was 49.85%.

[0066] Results analysis: The sorting efficiency of Application Examples 1-3 (pre-mixed) was 24.22%, 24.31% and 23.29% higher than that of Application Example 1, respectively, and was 8.80%, 8.70% and 9.58% higher than that of Application Examples 4-6 (mixed and added on the spot).

[0067] As can be seen from the above embodiments and comparative examples, the collector provided by the present invention can improve the flotation and separation effect of lepidolite when used in the flotation of lepidolite.

[0068] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A collector comprising octadecylamine and polyoxyethylene ether; The mass ratio of octadecylamine to polyoxyethylene ether is (5~15):

1.

2. The collector according to claim 1, characterized in that, The polyoxyethylene ether includes one or more of fatty alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, and fatty amine polyoxyethylene ether.

3. The collector according to claim 2, characterized in that, When the polyoxyethylene ether is a fatty alcohol polyoxyethylene ether, the mass ratio of the octadecylamine to the polyoxyethylene ether is (5~8):

1.

4. The collector according to claim 2, characterized in that, When the polyoxyethylene ether is octylphenol polyoxyethylene ether, the mass ratio of octadecylamine to polyoxyethylene ether is (5~8):

1.

5. The collector according to claim 2, characterized in that, When the polyoxyethylene ether is a fatty amine polyoxyethylene ether, the mass ratio of the octadecylamine to the polyoxyethylene ether is (10~13):

1.

6. A collector solution, obtained by mixing the collector according to any one of claims 1 to 5, an acid, and water.

7. The collector solution according to claim 6, characterized in that, The mass concentration of the acid is 36-38%, and the mass ratio of the acid to octadecylamine is (2-6):

1.

8. The application of the collector according to any one of claims 1 to 5 in the flotation of lepidolite.

9. The application according to claim 8, characterized in that, Based on the mass of lepidolite ore during lepidolite flotation, the amount of collector used is 200~400g / t.

10. The application according to claim 8 or 9, characterized in that, The applications include: Lithium mica ore is slurry prepared to obtain lithium mica slurry; The collector, acid, and water are mixed to obtain a collector solution; The collector solution and lepidolite slurry are mixed and then subjected to flotation.