A low-temperature resistant spodumene flotation collector, its preparation method and application

Abstract

The present invention relates to a low-temperature resistant spodumene flotation collector, a preparation method, and applications thereof. The collector comprises oleic acid, tall oil, sodium alkylbenzene sulfonate, and an emulsifier. The preparation method of the flotation collector comprises: heating the oleic acid, mixing it into the tall oil, stirring and mixing uniformly, then adding the sodium alkylbenzene sulfonate and mixing uniformly to obtain a mixture, then adding the emulsifier to the mixture, and stirring until the reaction is complete. The collector of the present invention has a wide material source and is low in price. The combination of oleic acid, tall oil, and sodium alkylbenzene sulfonate solves the problem of the spodumene collector dispersing in the ore pulp. The collector has excellent collection capacity and selectivity in low-temperature ore pulp, is beneficial for improving the grade and recovery rate of spodumene concentrate, and reduces fluctuations in flotation indicators caused by temperature changes. The collector has good adaptability to various types of spodumene ores in different altitudes. The collector is also beneficial for improving the grade and recovery rate of spodumene and stabilizing the flotation indicators of the mineral processing plant.

Description

Technical Field

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

[0002] Lithium is an essential and key raw material for the development of the new energy vehicle industry, holding a crucial strategic position. The secure supply of lithium resources is crucial to the healthy and stable development of strategic emerging industries such as new energy vehicles, energy storage, and electronic information. As living standards improve and urbanization becomes increasingly pronounced, the proportion of high-end new energy vehicle production is expected to increase further. The lithium required for the high-nickel ternary material used to power new energy vehicles is derived from spodumene, meaning that demand for spodumene will grow faster than the average level of lithium resources.

[0003] Due to factors such as technology and mining costs, hard rock lithium is currently primarily mined from granite pegmatite-type spodumene deposits in Xinjiang and Sichuan, and alkaline feldspar granite-type spodumene deposits in Jiangxi. Granite pegmatite spodumene is mostly mined in cold, high-altitude areas.

[0004] Existing spodumene flotation requires specific temperature conditions to achieve optimal flotation results. Traditional spodumene flotation uses fatty acid collectors, which are sensitive to flotation temperature. Their solubility and dispersibility decrease in water temperatures below 18°C, reducing their collection performance. Therefore, when water temperatures fall below 18°C ​​during autumn and winter, spodumene flotation requires slurry heating. Some high-altitude flotation plants even require slurry heating year-round, resulting in high flotation energy consumption and increased beneficiation costs.

[0005] Therefore, in order to overcome the shortcomings of traditional fatty acid collectors such as poor solubility, poor selectivity, sensitivity to low temperatures, large dosage of reagents, and low concentrate recovery rate, an efficient and low-temperature resistant spodumene flotation collector is urgently needed. Summary of the Invention

[0006] (1) Technical issues to be resolved

[0007] In order to solve the above problems in the prior art, the present invention provides a low-temperature resistant spodumene flotation collector, a preparation method and application thereof.

[0008] (2) Technical solution

[0009] In order to achieve the above objectives, the main technical solutions adopted by the present invention include:

[0010] A low-temperature resistant spodumene flotation collector comprises, by weight, 55-60 parts of oleic acid, 22-28 parts of tall oil, 3-5 parts of sodium alkylbenzene sulfonate and 12-16 parts of an emulsifier.

[0011] As described above, the low-temperature resistant spodumene flotation collector, preferably, the general structural formula of the sodium alkylbenzene sulfonate is R- -SO3Na, wherein the R group is a non-polar group, preferably a hydrocarbon chain, and the number of carbon atoms in the non-polar group is 12 to 18, that is, R = C12 to C18.

[0012] Furthermore, the most preferred sodium alkylbenzene sulfonate is one having a non-polar group with 12, 14, 16, or 18 carbon atoms.

[0013] In the low-temperature resistant spodumene flotation collector as described above, preferably, the emulsifier is one or more of polyoxyethylene ether sorbitan fatty acid ester (T-80), sorbitan monooleate (S-80), and triethanolamine.

[0014] More preferably, the emulsifier is a mixture of polyoxyethylene ether sorbitan fatty acid ester (T-80): sorbitan monooleate (S-80): triethanolamine in a weight ratio of 5.3-5.8:8.3-9.1:0.8-1.

[0015] The low-temperature-resistant spodumene flotation collector as described above preferably comprises 57.2 parts of oleic acid, 24.5 parts of tall oil, 3.9 parts of sodium alkylbenzene sulfonate, and 14.4 parts of emulsifier, and the sodium alkylbenzene sulfonate is sodium dodecylbenzene sulfonate.

[0016] The oleic acid can be commercially available industrial plant oleic acid, and the iodine value of the oleic acid is 130-180; the tall oil can be crude tall oil which is a by-product of the papermaking industry.

[0017] The method for preparing the low-temperature resistant spodumene flotation collector as described above preferably comprises the following steps:

[0018] A. Place oleic acid in a reactor and heat to 40-50°C, then slowly add tall oil and stir. Add sodium alkylbenzene sulfonate at 55-65°C, stir until completely dissolved, and mix thoroughly.

[0019] B. Add the emulsifier to the mixed material and continue stirring to obtain a brown oily substance which is the low-temperature resistant spodumene flotation collector.

[0020] In the preparation method as described above, preferably, in step A, the stirring time for both times is 20 to 30 minutes; and in step B, the stirring is continued for 30 to 60 minutes at a stirring rate of 200 to 500 r / min.

[0021] In the application of the low-temperature resistant spodumene flotation collector as described above in the flotation of spodumene, preferably, the temperature of the added water for flotation is 0-40°C; the temperature of the flotation slurry is 10-40°C, which can be applied to low temperatures of 10-20°C; the amount of the flotation collector is 400-2000g / t, most preferably 600-1200g / t.

[0022] A method for flotation of spodumene, comprising the steps of:

[0023] S1. Grinding the spodumene ore to a grinding fineness of -200 mesh accounting for 70-75%, and adding water to obtain a slurry;

[0024] S2. Add a pH adjuster and an activator to the pulp to adjust the pH to 11-13, add the flotation collector as described above to perform aeration flotation, scrape the foam to obtain spodumene roughing foam, and separate the scavenging pulp at the bottom of the tank;

[0025] S3. Blank selection is performed on the spodumene roughing foam to obtain spodumene concentrate.

[0026] In the method described above, preferably, in step S1, sodium carbonate is added to the spodumene ore or pulp, and the amount of sodium carbonate used is such that the pH of the pulp is adjusted to 8.0-8.5; and the amount of water added is such that the weight concentration of the pulp is 45%.

[0027] In the above method, preferably, in step S1, 30-40 g / t of cyclohexane soap is added to the ore pulp based on the original ore, and after stirring for 2-3 minutes, aeration flotation is performed to scrape the bubbles to obtain easily floating impurities, and the bottom of the tank is spodumene ore dressing pulp.

[0028] In the method described above, preferably, in step S2, the pH adjuster is sodium hydroxide, and the amount added is such that the pH value of the slurry is 11-13; the activator is calcium chloride, and the amount added is 0-150 g / t of raw ore; the stirring time is 25-35 min, and the stirring rate is 1900-2000 r / min.

[0029] In the method described above, preferably, in step S2, after stirring, the slurry concentration is adjusted to 30%, and a flotation collector is added in an amount of 400 to 2000 g / t. When the flotation collector is added, it is first prepared into an aqueous solution with a weight percentage concentration of 5 to 10% and then added.

[0030] Furthermore, preferably, the amount of the flotation collector used is 600 to 1200 g / t based on the original ore.

[0031] Preferably, in step S3, blank selection is performed without adding any reagents but only adding water, and the blank selection is divided into two times, wherein the first stage of blank selection needs to adjust the slurry concentration to 15-20%, stir for 2 minutes and then fill with air and scrape the foam, and the second stage of blank selection slurry concentration is 10-15%.

[0032] Blank concentration is a process in which low-concentration slurry utilizes residual reagents in the slurry and the stirring and aerating properties of the flotation machine to further remove gangue minerals in the coarse concentrate, further enrich useful minerals, and improve the grade of the concentrate. The preferred number of blank concentrations is two or more.

[0033] The method as described above preferably further comprises S4, adding the flotation collector as described above to the scavenging pulp at 30-200 g / t based on the original ore, stirring and then aerating for flotation, scraping the foam to obtain the scavenging foam product, and the bottom of the tank is the spodumene flotation tailings.

[0034] (3) Beneficial effects

[0035] The beneficial effects of the present invention are:

[0036] The present invention provides a low-temperature resistant spodumene flotation collector, which has strong collecting ability and selectivity under low-temperature conditions, has good adaptability to various spodumenes in different altitudes, and can stabilize the flotation index of the mineral processing plant.

[0037] The low-temperature resistant spodumene flotation collector provided by the present invention comprises raw materials including oleic acid, tall oil, sodium dodecylbenzenesulfonate and an emulsifier. The raw materials are widely available, have stable properties, are inexpensive and have low cost.

[0038] The low-temperature resistant spodumene flotation collector of the invention has mild preparation conditions, has good stability, and is suitable for mass production.

[0039] The low-temperature resistant spodumene flotation collector of the present invention is used for flotation of spodumene, which is beneficial to improving the grade and recovery rate of spodumene concentrate and reducing the fluctuation of flotation indicators caused by changes in latitude and altitude. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 Schematic diagram of the process of spodumene flotation separation in Example 1 of the present invention;

[0041] Figure 2 Schematic diagram of the process of spodumene flotation separation in Example 2 of the present invention;

[0042] Figure 3 Schematic diagram of the process of spodumene flotation separation in Example 3 of the present invention DETAILED DESCRIPTION

[0043] Temperature significantly impacts the flotation of spodumene using conventional collectors. At low temperatures, conventional collectors fail to disperse in the slurry, resulting in poor flotation foaming. This limits the selectivity and collection capabilities of the collectors, leading to low concentrate grade and recovery. Normal-temperature flotation generally occurs above 20°C, while low-temperature flotation typically occurs at temperatures between 14 and 18°C. Research has shown that oleic acid is a key collector in spodumene flotation. However, its use alone has drawbacks such as low solubility, poor low-temperature tolerance, poor selectivity, inability to tolerate hard water, poor dispersibility, and the high dosage required in flotation. Tal oil, a low-cost fatty acid collector, is also very important. Its collection performance is superior to oleic acid for carbonate-based ores, and its combination with oleic acid improves low-temperature tolerance. The combination of these two collectors produces co-adsorption, interacting with each other to promote and enhance mineral flotation.

[0044] Adding a small amount of anionic synergist or nonionic synergist to the collector for compounding can improve the characteristics of the agent, increase the recovery rate, improve the agent selectivity, and reduce the agent consumption compared with using it alone or with the simple addition effect. The present invention has found through a large number of experimental studies that the collection performance of oleic acid and tall oil can be enhanced by adding an appropriate amount of anionic synergist sodium dodecylbenzenesulfonate. The emulsifier uses nonionic synergists T-80 and S-80, both of which utilize different HLB (hydrophile-lipophile balance) values ​​to emulsify the collector, which can improve the dispersibility and water solubility of oleic acid and tall oil. Triethanolamine is then used to enhance the emulsifying effect of T-80 and S-80, so that the emulsifying effect remains long-lasting and is not easy to break. Oleic acid and tall oil compounded with emulsifiers can also reduce the amount of collector added by several times, thereby improving the recovery rate.

[0045] The collector is made by mixing and compounding the above ingredients. The material source is wide and the price is low. The compounding of oleic acid, tall oil and sodium alkylbenzene sulfonate solves the dispersion problem of the spodumene collector in the slurry. It has good collecting ability and selectivity in low-temperature slurry, which is beneficial to improving the grade and recovery rate of spodumene concentrate.

[0046] To better explain the present invention and facilitate understanding, the present invention is described in detail below in conjunction with the accompanying drawings through specific embodiments. Reagents used in the examples of the present invention that are not explicitly stated can all be commercially available conventional products. In the following examples, the Li2O content is assayed in accordance with the standard method of GB / T17413.1-2010; the slurry fineness is measured by wet sieving using a standard inspection sieve; the Li2O yield is measured by weighing and calculating different products; the Li2O recovery rate is calculated based on the Li2O grade and yield of the product, and the slurry concentration refers to the weight concentration of the ore in the ore and water.

[0047] Example 1

[0048] A low-temperature resistant spodumene flotation collector is prepared by preparing raw materials in a weight ratio of oleic acid: crude tall oil: sodium C12-18 alkylbenzene sulfonate: emulsifier of 57.2:24.5:3.9:14.4. The preparation method is as follows:

[0049] A. Weigh 57.2 parts of oleic acid, 24.5 parts of crude tall oil, and 3.9 parts of sodium dodecylbenzenesulfonate as raw materials by weight; stir the oleic acid in a water bath at 45°C, add the crude tall oil, and stir for 20 minutes; then add 3.9 parts of sodium dodecylbenzenesulfonate in a water bath at 60°C, stir for 20 minutes, and mix thoroughly until completely dissolved;

[0050] B. Weigh 5.3 parts of T-80 (polyoxyethylene ether sorbitan fatty acid ester), 8.3 parts of S-80 (sorbitan monooleate), and 0.8 parts of triethanolamine, mix and slowly add them to the above mixed materials, stir for 40 minutes, and obtain a brown oily substance which is the low-temperature resistant spodumene flotation collector. The stirring rate in A and B is 300r / min.

[0051] The flotation collector prepared above was used for flotation separation of spodumene ore. The spodumene ore used was from a concentrator in Yajiang County, Ganzi Prefecture, Sichuan Province. The spodumene ore contained 1.12% Li2O and was accompanied by tantalum-niobium ore. The gangue minerals were mainly quartz and feldspar, with other minerals such as tourmaline, biotite, chlorite, and garnet. The tantalum-niobium minerals were mainly tantalite-niobite isomorphous series minerals.

[0052] Flotation process such as Figure 1 As shown, Ganzi Prefecture is located in a high-altitude area with low temperatures throughout the year. In order to restore the low-temperature flotation environment of the concentrator, the flotation water in this embodiment is 0-4°C ice water frozen in a freezer. During the flotation process, ice bags are hung around the flotation tank to ensure that the following flotation test is carried out in a slurry environment of 10-15°C. After a period of easy floating, spodumene is subjected to one coarse, two fine, and one sweep, the easy floating does not participate in the circulation, and the middlings are returned in sequence. The specific operation is as follows:

[0053] (1) grinding the spodumene ore, adding the ore and sodium carbonate into the grinding mill, wherein the amount of sodium carbonate used is 1000 g / t based on the ore, the grinding concentration is 60%, the grinding fineness is -0.074 mm, accounting for 75%, and ice water is added to obtain a slurry with a slurry concentration of 45% and a pH of 8.5;

[0054] (2) Add 30 g / t of cyclohexane soap (Note: all t below are based on the weight of spodumene ore) to the slurry obtained in step (1), stir for 3 minutes, and then aerate for flotation. Scrape the bubbles to obtain easily floating impurities, and the bottom of the tank is spodumene ore dressing slurry.

[0055] (3) adding a pH adjusting agent, sodium hydroxide, and an activating agent, calcium chloride, to the spodumene ore dressing pulp of step (2), wherein the amount of sodium hydroxide is 1500 g / t, the amount of calcium chloride is 100 g / t, the stirring speed is 2000 r / min, and stirring is carried out for 30 min, at which time the pulp concentration is 45%, and the pulp pH value is 12. After stirring, ice water is added to adjust the pulp concentration to 30%, and the low-temperature resistant spodumene flotation collector prepared in Example 1 is added (the collector is 600 g / t based on the original ore, and the collector is added in an aqueous solution with a weight percentage concentration of 5%), stirring for 3 min, and then aerating flotation is carried out, and the foam is scraped to obtain spodumene roughing foam, and the bottom of the tank is divided into a scavenging ore dressing pulp;

[0056] (4) the roughing foam obtained in step (3) is subjected to two blank selections (blank selection is performed without adding any reagents but only adding water, wherein the first stage selection needs to adjust the pulp concentration to 15%, stir for 2 minutes and then perform air scraping, and the second stage selection pulp concentration is 10%), each selection scraping needs to be fully stirred for 2 minutes, and finally a spodumene concentrate product is obtained;

[0057] (5) Calcium chloride (20 g / t based on the original ore) was added to the scavenging pulp at the bottom of the tank in step (3), and after stirring for 2 minutes, the low-temperature resistant spodumene flotation collector prepared in Example 1 was added (the collector dosage was 120 g / t based on the original ore, and the collector was added in the form of a 5% by weight aqueous solution). After stirring for 3 minutes, aeration flotation was performed, and the scraping foam was the scavenging foam product, and the bottom of the tank was the spodumene flotation tailings.

[0058] The flotation results of spodumene obtained are shown in Table 1.

[0059] Table 1 Spodumene closed circuit test results

[0060]

[0061] Example 2

[0062] This embodiment provides a low-temperature resistant spodumene flotation collector, the weight ratio of the raw materials is:

[0063] Oleic acid: crude tall oil: sodium C12-18 alkylbenzene sulfonate: emulsifier are 60:22.1:3.5:14.4; the preparation method is as follows:

[0064] A. Weigh 60 parts of oleic acid, 22.1 parts of crude tall oil, and 3.5 parts of sodium dodecylbenzenesulfonate by weight. Stir the oleic acid in a water bath at 45°C, then slowly add the crude tall oil and stir for 20 minutes. Then, add 3.5 parts of sodium dodecylbenzenesulfonate in a water bath at 60°C, stir for 20 minutes, and mix thoroughly until completely dissolved.

[0065] B. Weigh 5.3 parts of T-80 (polyoxyethylene ether sorbitan fatty acid ester), 8.3 parts of S-80 (sorbitan monooleate), and 0.8 parts of triethanolamine, mix and slowly add them to the above mixed materials, stir for 30 minutes, and obtain a brown oily substance which is a low-temperature resistant spodumene flotation collector. The stirring rate in A and B is 300 r / min.

[0066] The flotation collector prepared as above is used for flotation separation of spodumene ore. The spodumene ore used is the spodumene mine in Dahongliutan, Hotan County, Xinjiang. The mine is located at an altitude of 5500m and has low temperatures all year round. The spodumene ore contains 1.43% Li2O, accompanied by tantalum-niobium ore. Other minerals are mainly quartz and potassium feldspar, sodium feldspar, iron lithium mica, biotite, sodium calcium feldspar, muscovite, etc.

[0067] The specific flotation process is as follows: Figure 2 As shown in the figure, due to the low temperature in the concentrator all year round, in order to restore the low-temperature flotation environment of the concentrator, the flotation water is 0-4℃ ice water frozen in a freezer. During the flotation process, ice bags are hung around the flotation tank to ensure that the following flotation test is carried out in a slurry environment of 10℃ to 14℃. After a period of easy floatation, spodumene is subjected to one coarse, two fine and one sweep, the easy floatation does not participate in the circulation, and the middlings are returned in sequence. The specific operation is as follows:

[0068] (1) Grinding the spodumene ore, adding the ore and sodium carbonate into the grinding mill, the amount of sodium carbonate is 1400g / t, the grinding concentration is 60%, the grinding fineness is -0.074mm, accounting for 70%, and ice water is added to adjust the pulp concentration to 45% and the pH value to 8.0;

[0069] (2) Add 35 g / t of cyclohexane soap (Note: all t below are based on the weight of spodumene ore) to the slurry obtained in step (1), stir for 3 minutes, and then aerate for flotation. Scrape the bubbles to obtain easily floating impurities, and the bottom of the tank is spodumene ore dressing slurry.

[0070] (3) adding a pH adjusting agent, sodium hydroxide, and an activating agent, calcium chloride, to the ore pulp of step (2), wherein the amount of sodium hydroxide is 800 g / t based on the original ore, the amount of calcium chloride is 80 g / t based on the original ore, the ore pulp concentration is 45%, the ore pulp pH value is 12, and the mixture is fully stirred for 30 minutes at a stirring rate of 2000 r / min. After the stirring is completed, ice water is added to adjust the ore pulp concentration to 30%, and the above-prepared low-temperature resistant spodumene flotation collector is added (the amount of the collector is 750 g / t based on the original ore, and the collector is first prepared into an aqueous solution with a weight percentage concentration of 5%, and then added according to the collector aqueous solution). After stirring for 3 minutes, aeration flotation is performed, and the foam is scraped to obtain spodumene roughing foam, and the bottom of the tank is divided into a scavenging slurry;

[0071] (4) The roughing foam obtained in step (3) is subjected to two blank selections (blank selection is performed without adding any reagents but only adding water, wherein the first stage selection needs to adjust the pulp concentration to 15%, stir for 2 minutes and then perform air scraping, and the second stage selection pulp concentration is 10%), each selection scraping needs to be fully stirred for 2 minutes, and finally a spodumene concentrate product is obtained;

[0072] (5) adding calcium chloride (10 g / t based on the original ore) to the scavenging pulp at the bottom of the tank in step (3), stirring for 2 minutes, and then adding the above-prepared low-temperature resistant spodumene flotation collector (the collector dosage is 100 g / t based on the original ore, and the collector is added in the form of a 5% weight percent aqueous solution), stirring for 3 minutes, and then aerating flotation, the scraping foam is the scavenging foam product, and the bottom of the tank is the spodumene flotation tailings.

[0073] The flotation results of spodumene are shown in Table 2.

[0074] Table 2 Spodumene closed circuit test results

[0075]

[0076] Example 3

[0077] This embodiment provides a low-temperature resistant spodumene flotation collector, the weight ratio of the raw materials is:

[0078] Oleic acid: crude tall oil: sodium C12-18 alkylbenzene sulfonate: emulsifier are 56.3:24.6:3.3:15.8; the preparation method is as follows:

[0079] A. Weigh 56.3 parts of oleic acid, 24.6 parts of crude tall oil, and 3.3 parts of sodium dodecylbenzenesulfonate by weight. Stir the oleic acid in a water bath at 45°C, add the crude tall oil, and stir for 20 minutes. Then, add the sodium dodecylbenzenesulfonate in a water bath at 60°C, stir for 20 minutes, and mix thoroughly until completely dissolved.

[0080] B. Weigh 5.8 parts of T-80 (polyoxyethylene ether sorbitan fatty acid ester), 9.1 parts of S-80 (sorbitan monooleate), and 0.9 parts of triethanolamine, mix and slowly add them to the above mixed materials, stir for 40 minutes, and obtain a brown oily substance which is a low-temperature resistant spodumene flotation collector. The stirring rate in A and B is 300 r / min.

[0081] The flotation collector prepared as described above was used for flotation separation of spodumene ore. The spodumene ore used was an Australian imported spodumene ore from a concentrator in Tangshan, Hebei. The ore contained 1.63% Li2O. The spodumene was gray-white crystals with columnar parallel cracks, as well as purple and dark brown lepidolite crystals. The surface was iron-stained, and the gangue minerals were mainly calcium-iron silicate minerals.

[0082] Flotation process such as Figure 3 As shown in the figure, in order to explore the flotation effect of the collector on the ore under low temperature environment, a flotation test was carried out under low temperature environment. The flotation water was 0-4℃ ice water frozen in a freezer. During the flotation process, ice bags were hung around the flotation tank to ensure that the slurry temperature was within the range of 14-18℃. The following flotation test was carried out in the slurry environment. The closed-circuit flotation process of spodumene with one coarse, two fines and one sweep, and the middlings were returned in sequence, and the specific operation is as follows:

[0083] (1) Grinding the spodumene ore, adding the ore and sodium carbonate into the grinding mill, the amount of sodium carbonate is 1000g / t, the grinding fineness is -0.074mm, accounting for 77%, adding ice water, adjusting the slurry concentration to 45%, and the slurry pH value to 8.5;

[0084] (2) adding sodium hydroxide as a pH adjuster and calcium chloride as an activator to the ore pulp of step (1), wherein the amount of sodium hydroxide is 800 g / t based on the original ore, and the amount of calcium chloride is 100 g / t based on the original ore, and the mixture is fully stirred for 30 min at a stirring rate of 2000 r / min. The pH value of the ore pulp is 12. After the stirring is completed, ice water is added to adjust the ore pulp concentration to 30%, and the above-prepared low-temperature resistant spodumene flotation collector is added (the amount of the collector is 550 g / t based on the original ore, and the collector is added in the form of a 5% by weight aqueous solution). After stirring for 3 min, aeration flotation is performed, and the foam is scraped to obtain spodumene roughing foam, and the bottom of the tank is divided into a scavenging slurry;

[0085] (3) The roughing foam obtained in step (2) is subjected to two blank selections (blank selection is performed without adding any reagents but only adding water, wherein the first stage selection needs to adjust the pulp concentration to 15%, stir for 2 minutes and then perform air scraping, and the second stage selection pulp concentration is 10%), each selection scraping needs to be fully stirred for 2 minutes, and finally a spodumene concentrate product is obtained;

[0086] (4) adding 30 g / t of calcium chloride to the scavenging pulp at the bottom of the tank in step (2), stirring for 2 min, and then adding the above-prepared low-temperature resistant spodumene flotation collector (the amount of the collector is 120 g / t based on the original ore, and the collector is added in the form of a 5% weight percent aqueous solution), stirring for 3 min, and then aerating flotation, the scraping foam is the scavenging foam product, and the bottom of the tank is the spodumene flotation tailings.

[0087] The flotation results of spodumene are shown in Table 3.

[0088] Table 3 Spodumene closed circuit test results

[0089]

[0090] From the flotation indices in Tables 1, 2, and 3 above, it can be seen that the low-temperature resistant spodumene flotation collector of the present invention has good collection ability and selectivity under low-temperature conditions, can obtain spodumene concentrate with high grade and recovery rate, has good adaptability to various types of spodumene ores in different altitudes, and can stabilize the flotation indicators of the mineral processing plant.

[0091] Comparative Example 1

[0092] The weight ratio of flotation collector in Comparative Example 1 is: oxidized paraffin soap: tall oil = 2:1, and the amount of collector used is 2.8 times that of the collector used in Example 1. The rest is the same as Example 1. The comparative flotation test results are shown in Table 4.

[0093] Table 4

[0094]

[0095]

[0096] As can be seen from the test results in Table 4, the Li2O grade and recovery rate of the lithium concentrate obtained by flotation using the collector prepared in Example 1 of the present invention are both better than those of the lithium concentrate obtained in Comparative Example 1. The reason is that the several raw materials of the present invention react during the heating process to generate a low-temperature resistant spodumene flotation collector; the collectors form a co-adsorption phenomenon, which produces an interaction. In addition, the addition of the anionic synergist and the non-ionic synergist enhances the dispersibility, water solubility, and low-temperature resistance of the collector and reduces the amount of the collector used, which is beneficial to the collection of spodumene at low temperatures.

[0097] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other manner. Any person skilled in the art may utilize the above-disclosed technical content to modify or modify the above-disclosed embodiments into equivalent embodiments. However, any simple modifications, equivalent variations, and modifications to the above-disclosed embodiments that do not depart from the technical content of the present invention and are based on the technical essence of the present invention shall remain within the scope of protection of the present invention.

Claims

1. A low-temperature resistant spodumene flotation collector, characterized in that: The invention is prepared from 57.2 parts of oleic acid, 24.5 parts of tall oil, 3.9 parts of sodium alkylbenzene sulfonate and 14.4 parts of an emulsifier in parts by weight; the emulsifier is a mixture of polyoxyethylene ether sorbitan fatty acid ester: sorbitan monooleate: triethanolamine in a weight ratio of 5.3-5.8:8.3-9.1:0.8-1; The low-temperature resistant spodumene flotation collector is obtained by the following preparation method: A. Heat oleic acid to 40-50°C, add tall oil and stir. Add sodium alkylbenzene sulfonate at 55-65°C, stir until completely dissolved, and mix thoroughly. B. Add emulsifier to the mixed material and continue stirring to obtain a brown oily substance which is a low-temperature resistant spodumene flotation collector; The general structural formula of the sodium alkylbenzene sulfonate is Wherein the R group is a non-polar group, R = C12; In step A, the stirring time is 20 to 30 minutes for each of the two times; in step B, the stirring is continued for 30 to 60 minutes.

2. The application of the low-temperature resistant spodumene flotation collector according to claim 1 in flotation of spodumene, characterized in that: The temperature of the added water for flotation is 0-40° C., the temperature of the flotation pulp is 10-40° C., and the dosage of the flotation collector is 400-2000 g / t.

3. A method for flotation of spodumene, characterized in that: It includes the following steps: S1. Grinding the spodumene ore to a grinding fineness of -200 mesh accounting for 70-75%, and adding water to obtain a slurry; S2. Add a pH adjuster and an activator to the slurry to adjust the pH to 11-13, stir and mix the slurry, add the flotation collector as claimed in claim 1 to perform aeration flotation, scrape the foam to obtain spodumene roughing foam, and separate the scavenging slurry at the bottom of the tank; S3, blank selection of the spodumene roughing foam to obtain spodumene concentrate; In step S1, sodium carbonate is added to the spodumene ore or slurry, the amount of sodium carbonate used is such that the pH value of the slurry is adjusted to 8.0-8.5, and the amount of water added is such that the mass concentration of the slurry is 40-45%; cyclohexane acid soap is added to the slurry at 30-40 g / t based on the ore, and the slurry is stirred for 2-3 minutes and then aerated for flotation, and the bubbles are scraped to obtain easily floating impurities, and the bottom of the tank is the spodumene ore dressing slurry; In step S2, the pH adjuster is sodium hydroxide, and the amount added is such that the pH value after slurry adjustment is 11-13; the activator is calcium chloride, and the amount added is 0-150 g / t based on the original ore; the stirring time is 25-35 minutes, and the stirring rate is 1900-2000 r / min; the amount of the flotation collector added is 400-2000 g / t based on the original ore; In step S3, the blank is selected by adding only water, stirring for 2 minutes, and then inflating with air and scraping.

4. The method according to claim 3, wherein It also includes S4, adding flotation collector to the scavenging pulp at 30 to 200 g / t based on the original ore, stirring and then aerating for flotation, scraping the foam to obtain the scavenging foam product, and the bottom of the tank is the spodumene flotation tailings.

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