A low-temperature spodumene collector and its preparation method and application

Abstract

The present invention belongs to the field of spodumene mineral flotation technology, and is specifically related to a low-temperature type spodumene collector and its preparation method and application. The collector is based on N-dodecanoyl sarcosine or N-oleoyl sarcosine as the main component, and auxiliary components such as ethylenediaminetetraacetic acid (EDTA), glycerol, and defoamer are added. After saponification, an appropriate amount of emulsifier and surfactant are added to form a composite, and it has good low-temperature fluidity, and can replace conventional fatty acid collectors such as traditional oleic acid, oxidized paraffin soap, tall oil, and naphthenic acid. The low-temperature type spodumene collector of the present invention has good collecting performance and selectivity to spodumene ore, and has good low-temperature resistance at the same time. Its preparation process has the technical advantages of being simple and easy to operate, and producing without three wastes, and is a kind of economic and environmentally friendly high-efficiency spodumene collector.

Description

Technical Field

[0001] The invention belongs to the technical field of spodumene mineral flotation, and in particular relates to a low-temperature spodumene collector and a preparation method and application thereof. Background Art

[0002] Lithium metal is not only an important energy metal that plays a significant role in the field of new energy batteries, but its alloys and compounds also have excellent properties and are widely used in special glass, functional ceramics, metallurgy, electronics, medicine and other fields. They are also used in cutting-edge technology fields such as atomic energy, aerospace and national defense.

[0003] Spodumene (LiAl(SO3)2) is an important lithium mineral resource. Flotation is often used to separate spodumene from useless gangue minerals to obtain high-quality spodumene concentrate. In the spodumene flotation process, the commonly used flotation agent is anionic flotation collector. Anionic collectors are mostly fatty acids and soaps containing long carbon chains. Their biggest drawback is poor low-temperature resistance, and their low-temperature resistance directly determines the reduction of their flotation performance in low-temperature environments. This is because at lower temperatures (<10°C), the solubility and fluidity of anionic collectors decrease, resulting in weaker dispersibility and foaming properties, which in turn reduces their collection performance. At present, most lithium mines are located in high altitudes or cold areas. Therefore, how to improve the low-temperature resistance of anionic flotation collectors has become an important direction that R&D personnel focus on.

[0004] In addition, the current anion flotation collector has the problems of large amount of collector (up to 2kg / t), poor effect when used alone, and contamination of the mineral surface (contamination by calcium and magnesium ions) leading to poor separation effect.

[0005] Therefore, there is an urgent need to develop a low-temperature resistant spodumene collector that takes into account both selectivity and green environmental protection and degradability, in order to obtain spodumene concentrate with good flotation indicators. Summary of the invention

[0006] In view of the above technical problems, the present invention provides a low-temperature spodumene collector and a preparation method and application thereof. The low-temperature spodumene collector provided by the present invention has good low-temperature resistance, good selectivity and strong collecting ability.

[0007] The present invention is achieved through the following technical solutions:

[0008] A method for preparing a low-temperature spodumene collector, the method comprising:

[0009] N-lauroylsarcosine or N-oleoylsarcosine is used as a main component, ethylenediaminetetraacetic acid (EDTA), glycerol, a defoamer and a sodium hydroxide solution are added for saponification, and an emulsifier and a surfactant are added after saponification for compounding to prepare a low-temperature spodumene collector.

[0010] Furthermore, the raw materials used to prepare the low-temperature spodumene collector include, by weight: 50-60 parts of N-lauroyl sarcosine or N-oleoyl sarcosine, 2 parts of ethylenediaminetetraacetic acid, 3-5 parts of glycerol, 1-2 parts of defoaming agent, 1 part of emulsifier, and 3-10 parts of surfactant.

[0011] Furthermore, the defoaming agent includes any one or more of tributyl phosphate, ethanol and butanol.

[0012] Furthermore, the emulsifier includes one or both of Tween-60 and Span-60.

[0013] Furthermore, the surfactant is a sulfate anion collector, an oxyethylene ether acid anion collector or an oxyethylene ether nonionic surfactant.

[0014] Furthermore, the sulfate anion collector is Turkey red oil, and the oxyethylene ether acid anion collector is fatty alcohol polyoxyethylene ether carboxylate AEC.

[0015] A low-temperature spodumene collector is prepared from the following raw materials in parts by weight: 50-60 parts of N-lauroylsarcosine or N-oleoylsarcosine, 2 parts of ethylenediaminetetraacetic acid, 3-5 parts of glycerol, 1-2 parts of defoaming agent, 1 part of emulsifier, and 3-10 parts of surfactant.

[0016] The invention discloses an application of a low-temperature spodumene collector, wherein the low-temperature spodumene collector is used for the flotation of spodumene under low-temperature conditions.

[0017] Furthermore, the flotation specifically comprises the following steps:

[0018] The spodumene is ground until the ore with a slurry particle size of -0.074 mm accounts for 60-65% of the total ore mass, sodium carbonate is added to adjust the slurry, sodium hydroxide is added for activation for 5-30 minutes, calcium chloride as a spodumene activator is added, and finally the low-temperature spodumene collector is added, and stirring and aeration flotation are performed to obtain a spodumene coarse concentrate.

[0019] The dosage of the sodium carbonate is 500-2000 g / t of spodumene ore; the dosage of the sodium hydroxide is 100-3000 g / t of spodumene ore; the dosage of the calcium chloride is 50-500 g / t of spodumene ore, and the dosage of the low-temperature spodumene collector is 100-2000 g / t of spodumene ore.

[0020] Beneficial technical effects of the present invention:

[0021] (1) The low-temperature spodumene collector provided by the present invention contains multiple active components, glycerol is used to improve low-temperature resistance, and surfactants are used to improve solubility and dispersibility. Therefore, the low-temperature spodumene collector provided by the present invention can help improve its solubility and dispersibility in aqueous solution under low temperature conditions, thereby improving its spodumene collection performance under low temperature conditions.

[0022] (2) The preparation method of the low-temperature spodumene collector provided by the present invention is simple, and there is no discharge of three wastes during the production process. At the same time, the low-temperature spodumene collector has the advantages of safe use, convenient addition, good selectivity (the Li2O grade corresponding to the spodumene concentrate is as high as 4.96%), etc. It can effectively replace the existing conventional fatty acid collectors such as oleic acid and oxidized paraffin soap, and effectively improve its collection ability and selectivity at low temperature (10°C).

[0023] (3) The low-temperature spodumene collector provided by the present invention can be used for the flotation of low-grade spodumene. Preferably, it is particularly suitable for the flotation technology of spodumene under low-temperature conditions, which is beneficial to improving the Li recovery rate and sorting index. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The present invention is a process flow chart of the application of a low-temperature spodumene collector in spodumene flotation. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0026] Further, in order to make the public have a better understanding of the present invention, some specific details are described in detail in the following detailed description of the present invention. For those skilled in the art, the present invention can be fully understood without the description of these details.

[0027] Example 1

[0028] A preparation method of a low-temperature spodumene collector comprises the following steps: adding 50 parts of N-lauroyl sarcosine, 2 parts of EDTA, 5 parts of glycerol and 2 parts of butanol defoaming agent, and then adding 30 parts of sodium hydroxide solution (concentration 25%) for saponification; after saponification for 30 minutes, adding 1 part of emulsifier Tween 80 and 10 parts of Turkish red oil, and stirring evenly to obtain the low-temperature resistant spodumene collector of the present invention.

[0029] Example 2

[0030] A preparation method of a low-temperature spodumene collector comprises the following steps: adding 50 parts of N-lauroyl sarcosine, 2 parts of EDTA, 5 parts of glycerol and 1 part of tributyl phosphate defoamer, and then adding 30 parts of sodium hydroxide solution (concentration 25%) for saponification; after saponification for 30 minutes, adding 1 part of emulsifier Tween 60 and 10 parts of Turkish red oil, and stirring evenly to obtain the low-temperature resistant spodumene collector of the present invention.

[0031] Example 3

[0032] A preparation method of a low-temperature spodumene collector comprises the following steps: adding 50 parts of N-oleoylsarcosine, 2 parts of EDTA, 5 parts of glycerol and 2 parts of butanol defoaming agent, and then adding 30 parts of sodium hydroxide solution (concentration 25%) for saponification; after saponification for 30 minutes, adding 1 part of emulsifier Tween 80 and 10 parts of Turkish red oil, and stirring evenly to obtain the low-temperature resistant spodumene collector of the present invention.

[0033] Example 4

[0034] A preparation method of a low-temperature spodumene collector comprises the following steps: adding 50 parts of N-oleoylsarcosine, 2 parts of EDTA, 5 parts of glycerol and 2 parts of tributyl phosphate defoaming agent, and then adding 30 parts of sodium hydroxide solution (concentration 25%) for saponification; after saponification for 30 minutes, adding 1 part of emulsifier Tween 60 and 10 parts of Turkish red oil, and stirring evenly to obtain the low-temperature resistant spodumene collector of the present invention.

[0035] Example 5

[0036] A preparation method of a low-temperature spodumene collector comprises the following steps: adding 60 parts of N-lauroyl sarcosine, 2 parts of EDTA, 3 parts of glycerol and 1 part of tributyl phosphate defoamer, and then adding 30 parts of sodium hydroxide solution (concentration 25%) for saponification; after saponification for 30 minutes, adding 1 part of emulsifier Span 60 and 3 parts of fatty alcohol polyoxyethylene ether carboxylates AEC; and stirring evenly to obtain the low-temperature resistant spodumene collector of the present invention.

[0037] Example 6

[0038] A preparation method of a low-temperature spodumene collector comprises the following steps: adding 60 parts of N-oleoylsarcosine, 2 parts of EDTA, 3 parts of glycerol and 1 part of butanol defoamer, and then adding 30 parts of sodium hydroxide solution (concentration 25%) for saponification; after saponification for 30 minutes, adding 1 part of emulsifier Tween 80 and 3 parts of fatty alcohol polyoxyethylene ether carboxylate AEC; and stirring evenly to obtain the low-temperature resistant spodumene collector of the present invention.

[0039] Spodumene flotation tests were carried out using the collectors invented in Examples 1 to 6 and conventional oleic acid collectors:

[0040] A spodumene mine was used as the ore to be floated, and the original ore contained 0.98% Li2O. Phase analysis results showed that the lithium mineral was mainly spodumene, accompanied by a small amount of lithium mica. Figure 1 As shown in the figure (in the figure, 1× means stirring for 1 min, 3× means stirring for 3 min, and 15× means stirring for 15 min), when the grinding fineness is -200 mesh, accounting for 65%, a roughing operation - a fine cleaning operation - a scavenging operation is performed; roughing operation: spodumene is ground to -0.074 mm, accounting for 60-65%, and then sodium carbonate is added for slurry adjustment, and then sodium hydroxide is added for activation for 5-30 min, and then calcium chloride, a spodumene activator, is added, and finally the low-temperature resistant spodumene collector prepared in Example 1-6 is added, and then stirred and aerated flotation is performed to obtain the corresponding spodumene coarse concentrate; wherein, the amount of sodium carbonate is 1000 g / t, the amount of sodium hydroxide is 500 g / t, the amount of activator calcium chloride is 150 g / t, and the amount of the collector prepared in Example 1 to 6 is 1000 g / t;

[0041] Sweeping operation: adding activator calcium chloride in an amount of 80 g / t and collector invented in Examples 1 to 6 in an amount of 200 g / t;

[0042] Selected operation: No chemicals are added. The experimental results are shown in Table 1.

[0043] Table 1 Experimental results of spodumene flotation using the collectors in Examples 1 to 6 and conventional oleic acid collectors (10-15°C)

[0044]

[0045]

[0046] As can be seen from Table 1, the spodumene collector prepared in the embodiment of the present invention can be used directly or in combination with other agents, has a strong collecting ability and selectivity for spodumene, can replace conventional collectors such as oleic acid, oxidized paraffin soap, and tall oil, and is beneficial to improving the sorting index.

[0047] The spodumene collector provided by the present invention has a good selective collection effect on spodumene at low temperature, can replace existing conventional fatty acid collectors such as oleic acid, oxidized paraffin soap, tall oil, cyclohexane acid, etc., can achieve good flotation technical indicators in actual ore flotation, and solves the defect of poor low temperature resistance of existing fatty acid collectors.

[0048] 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 principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a low-temperature spodumene collector, characterized in that: The method comprises: N-lauroylsarcosine or N-oleoylsarcosine is used as a main component, ethylenediaminetetraacetic acid, glycerol, a defoamer and a sodium hydroxide solution are added for saponification, and an emulsifier and a surfactant are added after saponification for compounding to prepare a low-temperature spodumene collector.

2. The preparation method of a low-temperature spodumene collector according to claim 1, wherein In parts by weight, the raw materials used to prepare the low-temperature spodumene collector include: 50-60 parts of N-lauroyl sarcosine or N-oleoyl sarcosine, 2 parts of ethylenediaminetetraacetic acid, 3-5 parts of glycerol, 1-2 parts of defoaming agent, 1 part of emulsifier, and 3-10 parts of surfactant.

3. according to the preparation method of a kind of low-temperature type spodumene collector described in claim 2, it is characterized in that, The defoaming agent includes any one or more of tributyl phosphate, ethanol and butanol.

4. according to the preparation method of a kind of low-temperature type spodumene collector described in claim 2, it is characterized in that, The emulsifier includes one or two of Tween-60 and Span-60.

5. according to the preparation method of a kind of low-temperature type spodumene collector described in claim 2, it is characterized in that, The surfactant is a sulfate anion collector, an oxyethylene ether acid anion collector or an oxyethylene ether nonionic surfactant.

6. The preparation method of a low-temperature spodumene collector according to claim 5, wherein: The sulfate anion collector is Türkiye red oil, and the oxyethylene ether acid anion collector is fatty alcohol polyoxyethylene ether carboxylate AEC.

7. A low-temperature spodumene collector, prepared by the method according to any one of claims 1 to 6, characterized in that: The low-temperature spodumene collector is prepared from the following raw materials in parts by weight: 50-60 parts of N-lauroylsarcosine or N-oleoylsarcosine, 2 parts of ethylenediaminetetraacetic acid, 3-5 parts of glycerol, 1-2 parts of defoaming agent, 1 part of emulsifier, and 3-10 parts of surfactant.

8. An application of a low-temperature spodumene collector, characterized in that: The low-temperature spodumene collector described in claim 7 is used for the flotation of spodumene under low temperature conditions of 10-15°C.

9. The application of a low-temperature spodumene collector according to claim 8, characterized in that: The flotation specifically comprises the following steps: The spodumene is ground until the ore with a slurry particle size of -200 mesh accounts for 60-65% of the total ore mass, sodium carbonate is added for slurry preparation, sodium hydroxide is added for activation for 5-30 minutes, calcium chloride as a spodumene activator is added, and finally the low-temperature spodumene collector is added, and the spodumene is stirred and aerated for flotation to obtain a spodumene coarse concentrate; In the roughing process, the dosage of the sodium carbonate is 500-2000 g / t of spodumene ore; the dosage of the sodium hydroxide is 100-3000 g / t of spodumene ore; the dosage of the calcium chloride is 50-500 g / t of spodumene ore, and the dosage of the low-temperature spodumene collector is 100-2000 g / t of spodumene ore.

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