Preparation of fatty hydroxamic acid for spodumene collecting agent and collecting agent and application thereof

Abstract

The invention discloses preparation of fatty hydroxamic acid for a spodumene collecting agent and the collecting agent and application of the fatty hydroxamic acid, a carboxylic acid compound and absolute ethyl alcohol are stirred and mixed at the normal temperature, then concentrated sulfuric acid is dropwise added under the condition of stirring at the normal temperature, heating reaction is carried out after the concentrated sulfuric acid is dropwise added, oil-water separation is carried out after the reaction is completed, and a carboxylic ester compound is obtained; the method comprises the following steps: adding hydroxylamine sulfate and water into a carboxylic ester compound, stirring and dissolving at normal temperature, slowly adding alkali under the condition of stirring at normal temperature, heating for reaction, neutralizing to be weakly acidic by using diluted hydrochloric acid after the reaction is finished, and separating a water phase to obtain a brown solution, namely the fatty hydroxamic acid. The spodumene collecting agent is prepared from the fatty hydroxamic acid, the fatty acid soap, the polyethylene glycol antifreezing agent and the emulsifying agent according to the proportion. The spodumene collecting agent is good in spodumene ore selectivity and high in collecting capacity.

Description

Technical Field

[0001] The invention relates to the technical field of mineral processing, and in particular to a fatty hydroxamic acid used for a spodumene collector, a preparation method thereof and application thereof in the spodumene collector. Background Art

[0002] Lithium is an important strategic resource, widely used in batteries, ceramics, glass, aluminum products, lubricants, refrigerants, nuclear industry and other industries. With the rapid development of strategic emerging industries such as new energy and new materials, the demand for lithium resources has gradually become prominent.

[0003] At present, the raw materials for the production of high-quality lithium products in my country mainly come from hard rock spodumene mines, and the main separation method is flotation. Since spodumene in the ore often coexists with silicate minerals such as feldspar, quartz and beryl, and they have similar surface chemical properties, it is difficult to separate spodumene from other silicate minerals. Spodumene flotation collectors are mainly divided into anionic collectors, cationic collectors and combined collectors. Anionic collectors mainly include fatty acids and fatty soap collectors such as oleic acid, oxidized paraffin soap, tall oil, and cyclopentane acid soap. Cationic collectors are mainly fatty amine collectors such as dodecylamine and octadecylamine. Combined collectors are mainly anionic combined collectors and anionic and cationic combined collectors. However, these collectors still have poor collection capacity and selectivity, and coarse-grained spodumene is easy to fall out of the tank. At the same time, there are problems such as high flotation foam viscosity, poor concentrate quality stability, and difficult on-site operation in the closed-circuit flotation process of spodumene oxide ore. Therefore, developing a collector with high selectivity and strong collection ability that can efficiently float coarse-grained spodumene is of great significance and value for achieving efficient utilization of hard rock lithium ore resources. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention aims to provide a preparation method of a fatty hydroxamic acid for a spodumene collector, a collector thereof and an application thereof.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] A method for preparing fatty hydroxamic acid used in a spodumene collector comprises the following steps:

[0007] S1, stirring and mixing a carboxylic acid compound and anhydrous ethanol at room temperature, then dropping concentrated sulfuric acid under stirring at room temperature, heating to react after the addition of concentrated sulfuric acid, and performing oil-water separation after the reaction to obtain a carboxylate compound;

[0008] S2. Add hydroxylamine sulfate and water to the carboxylate compound obtained in step S1, stir and dissolve at room temperature, then slowly add alkali under stirring at room temperature, then raise the temperature to react, and after the reaction is completed, neutralize with dilute hydrochloric acid to weak acidity, and remove the aqueous phase to obtain a brown solution that is fatty hydroxamic acid.

[0009] Furthermore, in step S1, the ratio of the carboxylic acid compound, anhydrous ethanol and concentrated sulfuric acid is 0.1 mol: 10 mL: 0.1 mL, and the mass concentration of the concentrated sulfuric acid is 98%; after the concentrated sulfuric acid is added dropwise, the temperature is raised to 60-80° C. and the reaction is carried out for 2-4 hours.

[0010] Furthermore, in step S1, the carboxylic acid compound includes at least one of cycloalkane acid and lauric acid.

[0011] Furthermore, in step S2, the molar ratio of the carboxylate compound, hydroxylamine sulfate and the base is 1:0.5:0.55-1.2; and the base is at least one of anhydrous sodium carbonate and sodium hydroxide.

[0012] Furthermore, in step S2, the reaction temperature is 50-70°C, and the reaction time is 4-8h; after the reaction is completed, it is neutralized with 5% dilute hydrochloric acid to a pH of 5-6.

[0013] The present invention also provides a fatty hydroxamic acid used in a spodumene collector prepared according to the preparation method.

[0014] The invention provides a spodumene collector, which comprises the following components calculated by mass percentage: 40-60% of fatty hydroxamic acid, 20-40% of fatty acid soap, 15-20% of polyethylene glycol antifreeze agent, and 2-5% of emulsifier; the fatty hydroxamic acid is prepared according to any one of the preparation methods described in claims 1-5.

[0015] Furthermore, the fatty acid soap is one of oxidized paraffin soap and sodium oleate.

[0016] Furthermore, the polyethylene glycol antifreeze agent includes at least one of polyethylene glycol-200 and polyethylene glycol-400.

[0017] Furthermore, the emulsifier includes at least one of dodecylphenol polyoxyethylene ether OP-10 and nonylphenol polyoxyethylene ether NP-10.

[0018] The present invention also provides an open circuit flotation method for spodumene, which specifically comprises the following steps:

[0019] A1. Grind spodumene to a fineness of -0.074mm and account for 65% of the dry weight of the ore per ton, and adjust the mass concentration of the flotation slurry to 30%;

[0020] A2. Firstly, a roughing operation is carried out, and the roughing concentrate obtained enters the third-level concentrating operation, and the roughing tailings enter the two-level scavenging operation; the concentrated concentrate obtained from each level of concentrating operation enters the next level of concentrating operation, and the concentrated concentrate obtained from the third level of concentrating operation is the concentrate 1; the scavenging tailings obtained from each level of scavenging operation enter the next level of scavenging operation, and the scavenging tailings obtained from the last scavenging operation are the final tailings;

[0021] In the roughing operation, Na2CO3, NaOH, CaCl2 and the above-mentioned spodumene collector are sequentially added to prepare the slurry; in the scavenging operation 1 and scavenging operation 2, CaCl2 and the above-mentioned spodumene collector are sequentially added; in the concentrating operation 1, concentrating operation 2 and concentrating operation 3, Na2CO3 is added;

[0022] A3. The tailings from each level of concentration and the scavenged concentrate from each level of scavenging are combined to carry out three-level scavenging operations. The scavenged concentrate from each level of scavenging enters the next level of scavenging. Na2CO3 is added in the scavenging operations one, two and three.

[0023] Further, based on the dry weight of each ton of raw ore, 800 g / t Na2CO3, 700 g / t NaOH, 150 g / t CaCl2 and 1500 g / t of the above-mentioned spodumene collector were added in sequence during the roughing operation, and the slurry mixing times were 5 min, 15 min, 5 min and 5 min, respectively;

[0024] In the scavenging operation 1 and scavenging operation 2, the amount of CaCl2 added was 75g / t and 30g / t respectively, the amount of spodumene collector added was 300g / t and 100g / t respectively, and the slurry mixing time was 5min;

[0025] In the first, second and third selection operations, the amount of Na2CO3 added was 400g / t, 200g / t and 100g / t respectively, and the slurry mixing time was 5min;

[0026] In the fine sweeping operation one, fine sweeping operation two and fine sweeping operation three, the amount of Na2CO3 added was 150g / t, 100g / t and 50g / t respectively, and the slurry mixing time was 5min.

[0027] The beneficial effects of the present invention are:

[0028] (1) The spodumene collector of the present invention has good selectivity for spodumene ore and strong collecting ability, and at the same time has good flotation recovery of coarse-grained spodumene, thereby achieving efficient flotation recovery of spodumene ore.

[0029] (2) The raw materials of the spodumene collector of the present invention are cheap and easily available, the preparation method is simple, and it is suitable for large-scale production, and has high promotion and application value.

[0030] (3) The collector open-circuit flotation method of spodumene of the present invention can solve the problems of poor concentrate quality stability and difficult on-site operation existing in the commonly used closed-circuit flotation process of oxidized ores. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a flotation process flow chart of Example 4 of the present invention and Comparative Example 1. DETAILED DESCRIPTION

[0032] The present invention will be further described below in conjunction with the accompanying drawings. It should be noted that this embodiment is based on the technical solution and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to this embodiment.

[0033] Example 1

[0034] Add 0.1 mol of cycloalkane acid and 10 mL of anhydrous ethanol to a 150 mL three-necked flask and stir at room temperature for 10 min, then add 0.1 mL of 98% concentrated sulfuric acid dropwise under room temperature stirring conditions, heat to 60°C after the addition is complete and react for 4 h, and separate the oil and water after the reaction is complete to obtain a cycloalkane ester compound. Add 0.1 mol of cycloalkane ester compound to a 150 mL three-necked flask, add 0.05 mol of hydroxylamine sulfate and 10 mL of water at room temperature and stir to dissolve, then slowly add 0.055 mol of anhydrous sodium carbonate under room temperature stirring conditions, heat to 70°C after the addition is complete and react for 4 h, neutralize with 5% dilute hydrochloric acid to pH = 5 after the reaction is complete, and separate the aqueous phase to obtain a brown solution, which is cycloalkane hydroxamic acid. Calculated by mass percentage, 40% of cycloalkanehydroxamic acid, 40% of oxidized paraffin soap, 15% of polyethylene glycol-400 antifreeze agent, and 5% of OP-10 emulsifier are uniformly mixed at room temperature to obtain a viscous liquid, which is the spodumene collector.

[0035] Example 2

[0036] Add 0.1 mol of cycloalkane acid and 10 mL of anhydrous ethanol to a 150 mL three-necked flask and stir at room temperature for 10 min, then add 0.1 mL of 98% concentrated sulfuric acid dropwise under room temperature stirring conditions, heat to 70°C after the addition, react for 3 h, and separate the oil and water after the reaction to obtain a cycloalkane ester compound. Add 0.1 mol of cycloalkane ester compound to a 150 mL three-necked flask, add 0.05 mol of hydroxylamine sulfate and 10 mL of water at room temperature and stir to dissolve, then slowly add 0.060 mol of anhydrous sodium carbonate under room temperature stirring conditions, heat to 50°C after the addition, react for 8 h, and neutralize with 5% dilute hydrochloric acid to pH = 5.5 after the reaction is completed. Separate the aqueous phase to obtain a brown solution, which is cycloalkane hydroxamic acid. Calculated by mass percentage, 60% cycloalkanehydroxamic acid, 20% sodium oleate, 17% polyethylene glycol-200 antifreeze agent, and 3% NP-10 emulsifier are uniformly mixed at room temperature to obtain a viscous liquid, which is the spodumene collector.

[0037] Example 3

[0038] Add 0.1 mol of lauric acid and 10 mL of anhydrous ethanol to a 150 mL three-necked flask and stir at room temperature for 10 min, then add 0.1 mL of 98% concentrated sulfuric acid dropwise under stirring at room temperature, heat to 80°C after the addition, react for 2 h, and separate the oil and water to obtain the lauric acid ester compound after the reaction. Add 0.1 mol of lauric acid ester compound to a 150 mL three-necked flask, add 0.05 mol of hydroxylamine sulfate and 10 mL of water at room temperature and stir to dissolve, then slowly add 0.12 mol of sodium hydroxide under stirring at room temperature, heat to 60°C after the addition, react for 6 h, neutralize with 5% dilute hydrochloric acid to pH=6 after the reaction, and separate the aqueous phase to obtain a brown solution, which is lauric acid hydroxamic acid. Calculated by mass percentage, 50% lauric acid, 28% oxidized paraffin soap, 20% polyethylene glycol-200 antifreeze agent, and 2% NP-10 emulsifier are uniformly mixed at room temperature to obtain a viscous liquid that is a spodumene collector.

[0039] Example 4

[0040] A hard rock type spodumene ore contains 1.53% Li2O grade, and the main impurities are feldspar and quartz, with contents of 39.11% and 33.74% respectively. According to the dry weight of the raw ore per ton, the spodumene is ground to a fineness of -0.074mm by a mill, accounting for 65%, and the flotation pulp concentration is adjusted to 30%. Then flotation is carried out through the process of "one roughing, three fine cleanings, two sweepings, and three fine sweepings". In the roughing, 800g / t Na2CO3 is added successively, and the slurry mixing time is 5min, 700g / t NaOH, and the slurry mixing time is 15min, 150g / t CaCl2, and the spodumene collector prepared in Example 1, and the slurry mixing time is 5min. In scavenging 1 and scavenging 2, the amount of CaCl2 added is 75g / t and 30g / t respectively, the amount of spodumene collector added in Example 1 is 300g / t and 100g / t respectively, and the slurry mixing time is 5min; in fine sweeping 1, fine sweeping 2 and fine sweeping 3, the amount of Na2CO3 added is 400g / t, 200g / t and 100g / t respectively, and the slurry mixing time is 5min; in fine sweeping 1, fine sweeping 2 and fine sweeping 3, the amount of Na2CO3 added is 150g / t, 100g / t and 50g / t respectively, and the slurry mixing time is 5min. In the lithium oxide concentrate (concentrate 1+concentrate 2) finally obtained, the Li2O grade is 6.30%, and the Li2O recovery rate is 88.12%. See flotation process Figure 1 The selection results are shown in Table 1.

[0041] Comparative Example 1

[0042] The difference between Comparative Example 1 and Example 4 is that the collector is different. The collector used in Comparative Example 1 is a combination collector of cyclohexane acid + oxidized paraffin soap in a weight ratio of 1:1. Other than this, the other flotation conditions are the same. In the lithium oxide concentrate (concentrate 1 + concentrate 2) finally obtained in this comparative example, the Li2O grade is 5.94% and the Li2O recovery rate is 82.80%. See the flotation process Figure 1 , the test results are shown in Table 1.

[0043] Table 1

[0044]

[0045] From the flotation results in Table 1, it can be seen that the flotation result of the modified spodumene collector provided in Example 1 for hard rock spodumene ore is better than that of the conventional unmodified cyclohexane acid + oxidized paraffin soap combined collector. At the same time, the spodumene collector provided in Example 1 is used, and the spodumene concentrate Li2O grade is 6.30%, and the Li2O recovery rate is 88.12%, which are excellent indicators, is obtained through the open-circuit flotation process of "one roughing, three cleaning, two scavenging, and three fine sweeping".

[0046] Example 5

[0047] A pegmatite spodumene ore contains 1.43% Li2O, and the main impurities are quartz and feldspar, with contents of 15.01% and 27.90% respectively. For the above ore, the spodumene collectors prepared in Examples 1-3 were used to carry out a roughing flotation test at room temperature, and compared with the conventional "oxidized paraffin soap + sodium oleate" anion combination collector and "oxidized paraffin soap + dodecylamine" cationic combination collector.

[0048] Based on the dry weight of the raw ore per ton, the spodumene was ground to a fineness of -0.074mm by a mill, accounting for 70%, and the flotation pulp concentration was adjusted to 30%. In the roughing, 800g / t Na2CO3 was added successively, the pulping time was 5min, 600g / t NaOH, the pulping time was 15min, 150g / t CaCl2, the pulping time was 5min, and 1000g / t collector, the pulping time was 5min. The test results are shown in Table 2.

[0049] Table 2

[0050]

[0051] It can be seen from the flotation results in Table 2 that the spodumene collectors of Examples 1-3 have good collecting ability and selectivity for pegmatite spodumene ore, and their flotation effects are better than those of the conventional "oxidized paraffin soap + sodium oleate" anionic combination collectors and "oxidized paraffin soap + dodecylamine" cationic combination collectors.

[0052] Example 6

[0053] For -0.2+0.1 mm coarse particle size spodumene pure mineral, a roughing flotation test was carried out using the spodumene collectors of Examples 1-3, respectively, and compared with the conventional "oxidized paraffin soap + sodium oleate" anionic combination collector and "oxidized paraffin soap + dodecylamine" cationic combination collector.

[0054] Take -0.2+0.1mm coarse-grained spodumene pure mineral, adjust the flotation pulp concentration to 20%; use NaOH to adjust the flotation pulp pH to 11.5, and the pulping time is 15 minutes; then add 20mg / L CaCl2 for 5 minutes, and 200mg / L collector for 5 minutes. The test results are shown in Table 3.

[0055] Table 3

[0056]

[0057] From the flotation results in Table 3, it can be seen that the spodumene collector has a good collection ability for -0.2+0.1mm coarse-grained spodumene pure minerals, and its flotation effect is better than that of the conventional "oxidized paraffin soap + sodium oleate" anionic combination collector and "oxidized paraffin soap + dodecylamine" cationic combination collector.

[0058] For those skilled in the art, various corresponding changes and modifications can be made according to the above technical solutions and concepts, and all of these changes and modifications should be included in the protection scope of the claims of the present invention.

Claims

1. A method for preparing a fatty hydroxamic acid used in a spodumene collector, characterized in that: The steps include: S1, stirring and mixing a carboxylic acid compound and anhydrous ethanol at room temperature, then dropping concentrated sulfuric acid under stirring at room temperature, heating to react after the addition of concentrated sulfuric acid, and performing oil-water separation after the reaction to obtain a carboxylate compound; S2. Add hydroxylamine sulfate and water to the carboxylate compound obtained in step S1, stir and dissolve at room temperature, then slowly add alkali under stirring at room temperature, then raise the temperature to react, and after the reaction is completed, neutralize with dilute hydrochloric acid to weak acidity, and remove the aqueous phase to obtain a brown solution that is fatty hydroxamic acid.

2. The preparation method according to claim 1, characterized in that: In step S1, the ratio of the carboxylic acid compound, anhydrous ethanol and concentrated sulfuric acid is 0.1 mol: 10 mL: 0.1 mL, and the mass concentration of the concentrated sulfuric acid is 98%; after the concentrated sulfuric acid is added dropwise, the temperature is raised to 60-80° C. and the reaction is carried out for 2-4 hours; the carboxylic acid compound includes at least one of cyclohexane acid and lauric acid.

3. The preparation method according to claim 1, characterized in that: In step S2, the molar ratio of the carboxylate compound, hydroxylamine sulfate and the base is 1:0.5:0.55-1.2; the base is at least one of anhydrous sodium carbonate and sodium hydroxide; the reaction temperature is 50-70°C, and the reaction time is 4-8h; after the reaction is completed, the reaction is neutralized with dilute hydrochloric acid with a mass concentration of 5% to a pH of 5-6.

4. A fatty hydroxamic acid used in a spodumene collector prepared by the preparation method according to any one of claims 1 to 3.

5. A spodumene collector, characterized in that, Calculated by mass percentage, the invention comprises the following components: 40-60% fatty acid hydroxamic acid, 20-40% fatty acid soap, 15-20% polyethylene glycol antifreeze agent, and 2-5% emulsifier; the fatty acid hydroxamic acid is prepared according to any one of the preparation methods described in claims 1-4.

6. The spodumene collector according to claim 5, wherein The fatty acid soap is one of oxidized paraffin soap and sodium oleate.

7. The spodumene collector according to claim 5, wherein The polyethylene glycol antifreeze agent includes at least one of polyethylene glycol-200 and polyethylene glycol-400.

8. The spodumene collector according to claim 5, wherein The emulsifier includes at least one of dodecylphenol polyoxyethylene ether OP-10 and nonylphenol polyoxyethylene ether NP-10.

9. An open circuit flotation method for spodumene, characterized in that: The specific steps include: A1. Grind spodumene to a fineness of -0.074mm and account for 65% of the dry weight of each ton of raw ore by a mill, and adjust the mass concentration of the flotation slurry to 30%; A2. Firstly, a roughing operation is carried out, and the roughing concentrate obtained enters the third-level concentrating operation, and the roughing tailings enter the two-level scavenging operation; the concentrated concentrate obtained from each level of concentrating operation enters the next level of concentrating operation, and the concentrated concentrate obtained from the third level of concentrating operation is the concentrate 1; the scavenging tailings obtained from each level of scavenging operation enter the next level of scavenging operation, and the scavenging tailings obtained from the last scavenging operation are the final tailings; In the roughing operation, Na2CO3, NaOH, CaCl2 and the spodumene collector described in any one of claims 5-8 are sequentially added to prepare the slurry; in the scavenging operation 1 and the scavenging operation 2, CaCl2 and the spodumene collector described in any one of claims 5-8 are sequentially added; in the concentrating operation 1, the concentrating operation 2 and the concentrating operation 3, Na2CO3 is added; A3. The tailings from each level of concentration and the scavenged concentrate from each level of scavenging are combined to carry out three-level scavenging operations. The scavenged concentrate from each level of scavenging enters the next level of scavenging. Na2CO3 is added in the scavenging operations one, two and three.

10. The open circuit flotation method according to claim 9, characterized in that: Based on the dry weight of the raw ore per ton, 800 g / t Na2CO3, 700 g / t NaOH, 150 g / t CaCl2 and 1500 g / t of the spodumene collector described in any one of claims 5 to 8 are added in sequence during the roughing operation, and the slurry mixing times are 5 min, 15 min, 5 min and 5 min respectively; In the scavenging operation 1 and the scavenging operation 2, the amount of CaCl2 added is 75 g / t and 30 g / t respectively, the amount of spodumene collector added in any one of claims 5-8 is 300 g / t and 100 g / t respectively, and the slurry mixing time is 5 min; In the first, second and third selection operations, the amount of Na2CO3 added was 400g / t, 200g / t and 100g / t respectively, and the slurry mixing time was 5min; In the fine sweeping operation one, fine sweeping operation two and fine sweeping operation three, the amount of Na2CO3 added was 150g / t, 100g / t and 50g / t respectively, and the slurry mixing time was 5min.

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