Composite extraction liquid, method for separating lithium and thallium, and method for extracting and preparing lithium products from lithium ore

Abstract

The present invention relates to a composite extraction solution, comprising an organic phosphoric acid, a phosphate ester and a diluent, and the molar ratio of the organic phosphoric acid to the phosphate ester is 1:0.2 - 1:0.5. The present invention also relates to a method for separating lithium from thallium, comprising: using the composite extraction solution to extract an acidic stock solution containing lithium ions and thallium ions, separating phases to obtain a thallium-loaded organic phase and a lithium-containing solution, and preparing a lithium product from the lithium-containing solution; performing back-extraction on the thallium-loaded organic phase, separating phases to obtain a thallium-containing solution and an unloaded composite extraction solution, and preparing a thallium product from the thallium-containing solution. The present invention also relates to a method for extracting and preparing a lithium product from a lithium ore, comprising: preparing an acidic leaching solution of the lithium ore; using the composite extraction solution to extract the leaching solution of the lithium ore, separating phases to obtain a thallium-loaded organic phase and a lithium-containing solution; and preparing a lithium product from the lithium-containing solution. The composite extraction solution of the present invention can selectively extract thallium ions from an acidic stock solution containing lithium ions and thallium ions, and has a good extraction effect.

Description

Technical Field

[0001] The present invention relates to the technical field of lithium preparation, and particularly to a composite extraction solution, a method for separating lithium from thallium, and a method for extracting and preparing lithium products from lithium ores. Background Art

[0002] Thallium (Tl) is a highly toxic rare and dispersed metal element. In nature, thallium often occurs as a trace element associated with oxidized ores such as feldspar, mica, and jarosite. During the mining, ore dressing, and smelting processes of these ores, serious thallium pollution will be generated.

[0003] For example, lithium mica usually contains trace amounts of thallium elements. During the process of extracting lithium, thallium elements will enter the flue gas and lithium leaching solution. This will not only cause thallium ions to be contained in the flue gas wastewater and the mother liquor after lithium extraction, seriously affecting the environment, but also a small amount of thallium ions will be mixed in lithium products such as lithium carbonate, affecting the product quality. However, when the lithium leaching solution contains both lithium ions and thallium ions at the same time, it is very difficult for traditional extraction and other processes to separate lithium ions and thallium ions. Moreover, thallium ions are associated elements with low content, and it is very difficult to treat them below the environmental protection standards. Therefore, it is extremely difficult to deal with thallium pollution. Summary of the Invention

[0004] Based on this, in view of the above problems, it is necessary to provide a composite extraction solution, a method for separating lithium from thallium, and a method for extracting and preparing lithium products from lithium ores. The composite extraction solution can selectively extract thallium ions from an acidic stock solution containing lithium ions and thallium ions, and has a very good extraction effect.

[0005] To achieve the above object, the technical solution adopted by the present invention is: a composite extraction solution, which includes an organic phosphoric acid, a phosphoric acid ester, and a diluent, and the molar ratio of the organic phosphoric acid to the phosphoric acid ester is 1:0.2 - 1:0.5. The composite extraction solution is used to selectively extract thallium ions from a stock solution containing lithium ions and thallium ions, wherein the stock solution is an acidic solution.

[0006] In one embodiment, the organic phosphoric acid is selected from at least one of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid, bis(2-ethylhexyl) phosphoric acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, dialkyldithiophosphinic acid, bis(2,4,4-trimethylpentyl) phosphinic acid, bis(diethyldithiophosphoric acid), di-n-butyldithiophosphoric acid, bis(2,4,4-trimethylpentyl) thiophosphoric acid, and bis(2-ethylhexyl) dithiophosphoric acid.

[0007] In one embodiment, the phosphate ester is selected from at least one of bis(2-ethylhexyl) phosphate, 2-ethylhexyl 2-ethylhexyl phosphate monoester, dibutyl dithiophosphate, tricresyl phosphate, butyldiphenyl phosphate, and trioctyl phosphate.

[0008] The present invention also provides a method for separating lithium from thallium, comprising the following steps:

[0009] Providing a stock solution containing lithium ions and thallium ions, wherein the stock solution is an acidic solution;

[0010] Extracting the stock solution with the composite extractant described above, separating phases to obtain a thallium-loaded organic phase and a lithium-containing solution, and preparing a lithium product from the lithium-containing solution;

[0011] Performing back-extraction on the thallium-loaded organic phase, separating phases to obtain a thallium-containing solution and an empty composite extractant, and preparing a thallium product from the thallium-containing solution.

[0012] In one embodiment, in the step of extracting the stock solution with the composite extractant described above, the molar ratio of the organic phosphoric acid in the composite extractant to the thallium ions in the stock solution is greater than or equal to 1.1:1;

[0013] And / or, the temperature is from -5°C to 50°C.

[0014] In one embodiment, the empty composite extractant is recycled for extracting the stock solution.

[0015] The present invention also provides a method for extracting and preparing a lithium product from lithium ore, comprising the following steps:

[0016] Preparing an acidic leaching solution of lithium ore;

[0017] Extracting the lithium ore leaching solution with the composite extractant described above, separating phases to obtain a thallium-loaded organic phase and a lithium-containing solution;

[0018] Preparing a lithium product from the lithium-containing solution.

[0019] In one embodiment, the lithium ore leaching solution is prepared by a roasting method, and the flue gas generated during the roasting process is absorbed and treated to obtain wastewater, and the wastewater is mixed into the lithium ore leaching solution.

[0020] In one embodiment, in the step of extracting the lithium ore leaching solution with the composite extractant described above, the molar ratio of the organic phosphoric acid in the composite extractant to the thallium ions in the lithium ore leaching solution is greater than or equal to 1.1:1;

[0021] And / or, the temperature is from -5°C to 50°C.

[0022] In one of the embodiments, the step further includes: performing back extraction on the thallium-loaded organic phase, separating phases to obtain a thallium-containing solution and an organic composite extract without load, and recycling the organic composite extract without load to extract the lithium ore leaching solution.

[0023] According to the ionic characteristics of thallium ions and lithium ions, by selecting organic phosphoric acid and phosphoric acid ester with a specific molar ratio as a synergistic extraction system, the present invention can selectively extract thallium ions from an acidic stock solution containing lithium ions and thallium ions, so as to selectively separate lithium ions and thallium ions, and the efficiency of selectively extracting thallium ions is very high and the effect is very good.

[0024] Therefore, in industrial production, the composite extract of the present invention can be well used for the separation of lithium and thallium. On the one hand, it can avoid or effectively reduce the inclusion of thallium ions in lithium products, affecting the quality of lithium products. On the other hand, it can avoid or effectively reduce thallium pollution to the environment. For example, when extracting and preparing lithium products from lithium ore, the composite extract of the present invention can be first used to extract and treat the lithium ore leaching solution to separate thallium ions in the lithium ore leaching solution, thereby avoiding or effectively reducing thallium pollution to the environment and improving the quality of lithium products at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a process flow chart of the method for separating lithium and thallium of the present invention;

[0026] Figure 2 is a process flow chart of extracting and preparing lithium products from lepidolite of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0027] For ease of understanding of the present invention, the present invention will be described more comprehensively below with reference to related embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided so that the understanding of the disclosure of the present invention is more thorough and comprehensive.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0029] Due to the ionic characteristics of lithium ions and thallium ions, it is difficult to separate the two with traditional extraction systems. Moreover, due to the content of thallium ions, it is difficult to completely remove thallium ions. Therefore, the present invention provides a composite extraction solution, which includes organophosphoric acid, phosphate ester, and diluent, and the molar ratio of the organophosphoric acid to the phosphate ester is 1:0.2 - 1:0.5. Thus, by selecting organophosphoric acid and phosphate ester with a specific molar ratio to synergistically act as an extraction system, thallium ions can be selectively extracted from the acidic stock solution containing lithium ions and thallium ions, and then lithium ions and thallium ions can be selectively separated, and the extraction effect of thallium ions is very good.

[0030] Optionally, the organophosphoric acid is selected from at least one of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid, bis(2-ethylhexyl) phosphoric acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, dialkyldithiophosphinic acid, bis(2,4,4-trimethylpentyl) phosphinic acid, bis(diethyldithiophosphoric acid), di-n-butyldithiophosphoric acid, bis(2,4,4-trimethylpentyl) thiophosphoric acid, and bis(2-ethylhexyl) dithiophosphoric acid.

[0031] Optionally, the phosphate ester is selected from at least one of bis(2-ethylhexyl) phosphate ester, 2-ethylhexyl phosphate mono-2-ethylhexyl ester, dibutyl dithiophosphate, tricresyl phosphate, butyldiphenyl phosphate, and trioctyl phosphate.

[0032] In the composite extraction solution of the present invention, the organophosphoric acid and the phosphate ester can be a combination of any of the above several types, such as: a combination of one organophosphoric acid and one phosphate ester, a combination of one organophosphoric acid and two or more phosphate esters, a combination of two or more organophosphoric acids and one phosphate ester, a combination of two or more organophosphoric acids and two or more phosphate esters; the molar ratio includes but is not limited to 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, etc.

[0033] Optionally, the diluent is selected from at least one of n-hexane, n-dodecane, cyclohexane, D70 special solvent oil, D80 special solvent oil, solvent oil No. 120, solvent oil No. 160, solvent oil No. 200, ordinary kerosene, aviation kerosene, and sulfonated kerosene.

[0034] Based on this, as Figure 1 shown, the present invention provides a method for separating lithium and thallium, including the following steps:

[0035] Provide a stock solution containing lithium ions and thallium ions, wherein the stock solution is an acidic solution;

[0036] Use the above-mentioned composite extraction solution to extract the stock solution, phase-separate to obtain a thallium-loaded organic phase and a lithium-containing solution, and prepare a lithium product from the lithium-containing solution;

[0037] The thallium-loaded organic phase is subjected to back-extraction, and after phase separation, a thallium-containing solution and an empty composite extractant solution are obtained. A thallium product is prepared from the thallium-containing solution.

[0038] Among them, the stock solution containing lithium ions and thallium ions can be any mixed solution containing lithium ions and thallium ions in industrial production, such as lithium ore leaching solution, lithium battery waste leaching solution, lithium precipitation mother liquor, etc.

[0039] In the step of extracting the feed solution containing lithium ions and thallium ions with the composite extractant described above, the extraction equipment can be selected from extraction clarifiers, static mixers, rotary extraction towers, etc. During extraction, control the molar ratio of the organic phosphoric acid in the composite extractant to the thallium ions in the stock solution to be greater than or equal to 1.1:1, specifically such as 1.1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 10:1, etc. The volume ratio of the composite extractant to the stock solution is 1:1 - 1:10, specifically such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc. All are beneficial to improving the extraction efficiency and extraction effect of thallium ions. The actual molar ratio and extraction volume ratio can be adjusted according to the extraction effect. Specifically, the extraction can be completed within 2 minutes.

[0040] The step of extracting the stock solution with the composite extractant described above can be carried out under normal pressure, and the temperature is not limited. Industrial production can be carried out in any production area. Of course, when the temperature during extraction is controlled within the range of -5°C to 50°C, it is also beneficial to improve the extraction efficiency and extraction effect of thallium ions.

[0041] Under comprehensively optimized conditions, the step of extracting the stock solution with the composite extractant described above can complete the extraction within 30 seconds.

[0042] After the extraction is completed, there are no restrictions on the step of back-extracting the thallium-loaded organic phase. During back-extraction, the back-extraction solution is an acidic solution, or the thallium-loaded organic phase is mixed with water and an acidic gas for back-extraction, where the acidic gas is continuously introduced. Optionally, the acidic solution can be hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, etc., and the acidic gas is selected from carbon dioxide, sulfur dioxide, chlorine, hydrogen chloride gas, etc.

[0043] After back-extraction, the empty composite extractant solution can be recycled for extracting the stock solution.

[0044] After obtaining the lithium-containing solution and thallium-containing solution, there are no restrictions on the methods for preparing lithium products from the lithium-containing solution and thallium products from the thallium-containing solution. For example, the lithium-containing solution can be treated by evaporation concentration process, extraction-stripping process, and freezing nitre process. The thallium-containing solution can obtain salt products by evaporation concentration, or can prepare thallium sulfide precipitate by adding sodium hydroxide and sodium sulfide.

[0045] When preparing lithium products using the lithium-containing solution of the present invention, there is almost no entrainment of thallium ions in the lithium products, and the product quality is significantly improved. In addition, in the mother liquor after preparing lithium products from the lithium-containing solution, the content of thallium ions is lower than 5 ppb, effectively reducing thallium pollution to the environment.

[0046] Specifically, the present invention also provides a method for extracting and preparing lithium products from lithium ore, including the following steps:

[0047] Prepare an acidic leaching solution of lithium ore;

[0048] Use the compound extraction solution described above to extract the lithium ore leaching solution, and separate phases to obtain a thallium-loaded organic phase and a lithium-containing solution;

[0049] Prepare lithium products from the lithium-containing solution.

[0050] The step of using the compound extraction solution to extract the lithium ore leaching solution can refer to the above step of using the compound extractant to extract the stock solution. The extraction equipment can be selected from extraction clarifiers, static mixers, rotary extraction towers, etc. During extraction, control the molar ratio of the organic phosphoric acid in the compound extraction solution to the thallium ions in the lithium ore leaching solution to be 1.1:1 - 2:1, and the volume ratio of the compound extraction solution to the lithium ore leaching solution to be 1:1 - 1:10. The extraction step can be carried out under normal pressure, and the temperature is not limited. It is preferably controlled within the range of -5°C to 50°C. The extraction can be completed within 2 minutes, and even can be completed within 30 seconds.

[0051] When the present invention uses a compound extraction solution to extract and prepare lithium products from lithium ore, a thallium-loaded organic phase is obtained by phase separation. Therefore, the step further includes: stripping the thallium-loaded organic phase, and separating phases to obtain a thallium-containing solution and an empty compound extraction solution, wherein the empty compound extraction solution is recycled for extracting the lithium ore leaching solution, and the thallium-containing solution is used to prepare thallium products.

[0052] For the method of extracting and preparing lithium products from lithium ore of the present invention, the lithium ore is preferably lepidolite with a high content of thallium element.

[0053] There are many methods for preparing lithium ore into lithium ore leaching solution, and the present invention does not limit them. Currently, the commonly used method is the roasting method. When preparing the lithium ore leaching solution by the roasting method, flue gas will be generated during the roasting process, and thallium will also be contained in the flue gas. The present invention preferably absorbs and treats the flue gas generated during the roasting process to obtain wastewater. The wastewater can be treated separately with a composite extractant, or the wastewater can be mixed into the lithium ore leaching solution, which will not have a substantial impact on the preparation of lithium products from the lithium ore leaching solution. However, it should be noted that the wastewater needs to be an acidic solution.

[0054] The present invention does not limit the method for absorbing and treating flue gas. Optionally, water spray absorption towers, resins, activated carbon, molecular sieves, etc. can be used for absorption.

[0055] Specifically, as Figure 2 shown, when lepidolite is mixed with sulfate and roasted, crushed, and leached in sequence, and after separating to obtain the leaching solution, if the thallium ions in the leaching solution are not treated, the content of thallium ions in the mother liquor after preparing lithium products can reach several hundred to several thousand ppb. After being treated by the process of the present invention, the content of thallium ions can be reduced to less than 5 ppb. In addition, after the flue gas is absorbed and treated by a water spray absorption tower, the concentration of thallium in the wastewater can also reach several hundred to several thousand ppb. Currently, methods such as precipitation for treatment have poor effects, and the concentration after treatment can still reach several hundred ppb. After the flue gas wastewater of the present invention is combined with the leaching solution for treatment, the content of thallium ions can be reduced to less than 5 ppb.

[0056] Hereinafter, the composite extraction solution, the method for separating lithium and thallium, and the method for extracting and preparing lithium products from lithium ore will be further described through the following specific examples.

[0057] Reference example

[0058] Take 500 g of lepidolite concentrate. Mix the lepidolite concentrate, sodium sulfate, and calcium oxide in a mass ratio of 1:0.45:0.8, roast at 900 °C for 4 h, then crush the roasted product, dissolve it in water at a solid-liquid ratio of 1:1, stir for 30 min and then stand for suction filtration. Perform three-stage leaching on the slag, and combine the filtrates to obtain 3.2 L of leaching solution. The lithium ion content is about 10 g / L, the thallium content is about 3690 ppb, PH = 5. The leaching solution is successively defluorinated with calcium oxide and resin, and calcium is removed with sodium carbonate to obtain a purified solution. The purified solution is then evaporated and concentrated for lithium precipitation to obtain 138.84 g of lithium carbonate and 2.845 L of lithium precipitation mother liquor. The lithium precipitation mother liquor is acidified and then concentrated again and returned to the purified solution.

[0059] After analysis, the concentration of thallium ions in the lithium precipitation mother liquor is 4150 ppb, and the lithium content is 2.015 g / L.

[0060] It can be seen that this lithium extraction process will cause thallium to continuously accumulate in the mother liquor of lithium precipitation, resulting in an increasing thallium concentration in the entire production system, which will affect production and wastewater discharge.

[0061] Example 1

[0062] The difference between Example 1 and the reference example is that 0.6 L of the composite extraction solution is mixed with the leaching solution, and after shaking extraction for 2 min, 3.2 L of the lithium-containing solution and 0.6 L of the thallium-loaded organic phase are separated. Then, the lithium-containing solution is successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation is carried out to obtain 139.61 g of lithium carbonate and 2.80 L of the mother liquor of lithium precipitation.

[0063] Among them, the composite extraction solution in this example includes 2,2'-methylene-bis(4,6-di-tert-butylphenyl) phosphoric acid, bis(2-ethylhexyl) phosphate, and kerosene. The molar ratio of 2,2'-methylene-bis(4,6-di-tert-butylphenyl) phosphoric acid to bis(2-ethylhexyl) phosphate is 1:0.3, and the volume ratio of kerosene is 50%.

[0064] After analysis, the concentration of thallium ions in the mother liquor of lithium precipitation is 2.1 ppb, and the lithium content is 1.995 g / L.

[0065] 10% hydrochloric acid is used for back-extraction of the thallium-loaded organic phase, the volume ratio is 1:5, and the back-extraction time is 2 min to obtain a thallium-containing back-extraction solution and an empty composite extraction solution. The empty composite extraction solution is recycled to the extraction stage for continued use. After detection, the thallium content in the thallium-containing back-extraction solution is 98.26 ppm, and lithium is not detected.

[0066] Example 2

[0067] The difference between Example 2 and the reference example is that 0.7 L of the composite extraction solution is mixed with the leaching solution, and after shaking extraction for 1 min, 3.2 L of the lithium-containing solution and 0.7 L of the thallium-loaded organic phase are separated. Then, the lithium-containing solution is successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation is carried out to obtain 138.17 g of lithium carbonate and 2.79 L of the mother liquor of lithium precipitation.

[0068] Among them, the composite extraction solution in this example includes bis(2-ethylhexyl) phosphate, 2-ethylhexyl phosphate mono-2-ethylhexyl ester, and kerosene. The molar ratio of bis(2-ethylhexyl) phosphate to 2-ethylhexyl phosphate mono-2-ethylhexyl ester is 1:0.45, and the volume ratio of kerosene is 45%.

[0069] After analysis, the concentration of thallium ions in the mother liquor of lithium precipitation is 1.9 ppb, and the lithium content is 2.10 g / L.

[0070] The thallium-loaded organic phase was stripped with 10% hydrochloric acid at a volume ratio of 1:5 for 2 min to obtain a thallium-containing stripping solution and an empty composite extraction solution. The empty composite extraction solution was recycled to the extraction stage for continuous use. After detection, the thallium content in the thallium-containing stripping solution was 84.21 ppm, and lithium was not detected.

[0071] Example 3

[0072] The difference between Example 3 and the reference example is that 0.8 L of the composite extraction solution was mixed with the leaching solution, shaken and extracted for 30 s, and then 3.2 L of the lithium-containing solution and 0.8 L of the thallium-loaded organic phase were separated. Then, the lithium-containing solution was successively subjected to impurity removal, purification, evaporation and concentration, etc., and then lithium precipitation was carried out to obtain 140.14 g of lithium carbonate and 2.805 L of the mother liquor after lithium precipitation.

[0073] Among them, the composite extraction solution in this example includes ethylenediaminetetramethylenephosphonic acid, dibutyl dithiophosphate and kerosene. The molar ratio of ethylenediaminetetramethylenephosphonic acid, dibutyl dithiophosphate and kerosene is 1:0.35, and the volume ratio of kerosene is 55%.

[0074] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation was 1.2 ppb, and the lithium content was 1.956 g / L.

[0075] The thallium-loaded organic phase was stripped with 10% hydrochloric acid at a volume ratio of 1:5 for 2 min to obtain a thallium-containing stripping solution and an empty composite extraction solution. The empty composite extraction solution was recycled to the extraction stage for continuous use. After detection, the thallium content in the thallium-containing stripping solution was 73.3 ppm, and lithium was not detected.

[0076] Example 4

[0077] The difference between Example 4 and the reference example is that 1 L of the composite extraction solution was mixed with the leaching solution, shaken and extracted for 30 s, and then 3.2 L of the lithium-containing solution and 1 L of the thallium-loaded organic phase were separated. Then, the lithium-containing solution was successively subjected to impurity removal, purification, evaporation and concentration, and ion exchange, etc., and then lithium precipitation was carried out to obtain 139.96 g of lithium carbonate and 2.857 L of the mother liquor after lithium precipitation.

[0078] Among them, the composite extraction solution in this example includes dialkyldithiophosphinic acid, tricresyl phosphate and kerosene. The molar ratio of dialkyldithiophosphinic acid and tricresyl phosphate is 1:0.25, and the volume ratio of kerosene is 60%.

[0079] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation was 1.0 ppb, and the lithium content was 1.932 g / L.

[0080] The thallium-loaded organic phase was stripped with 5% hydrochloric acid at a volume ratio of 1:5 for 2 minutes to obtain a thallium-containing stripping solution and an empty composite extraction solution. The empty composite extraction solution was recycled to the extraction stage for continued use. After detection, the thallium content in the thallium-containing stripping solution was 59 ppm, and lithium was not detected.

[0081] Example 5

[0082] The difference between Example 5 and the reference example is that 1.6 L of the composite extraction solution was mixed with the leaching solution, shaken and extracted for 20 s, and then 3.2 L of the lithium-containing solution and 1.6 L of the thallium-loaded organic phase were separated. Then, the lithium-containing solution was successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation was carried out to obtain 139.50 g of lithium carbonate and 2.775 L of the mother liquor after lithium precipitation.

[0083] Among them, the composite extraction solution in this example includes di-n-butyldithiophosphoric acid, trioctyl phosphate and kerosene. The molar ratio of di-n-butyldithiophosphoric acid to trioctyl phosphate is 1:0.5, and the volume fraction of kerosene is 50%.

[0084] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation was 1.0 ppb, and the lithium content was 2.021 g / L.

[0085] The thallium-loaded organic phase was stripped with 5% hydrochloric acid at a volume ratio of 1:10 for 1 minute to obtain a thallium-containing stripping solution and an empty composite extraction solution. The empty composite extraction solution was recycled to the extraction stage for continued use. After detection, the thallium content in the thallium-containing stripping solution was 73.5 ppm, and lithium was not detected.

[0086] Example 6

[0087] The difference between Example 6 and the reference example is that 0.5 L of the composite extraction solution was mixed with the leaching solution, shaken and extracted for 30 s, and then 3.2 L of the lithium-containing solution and 0.5 L of the thallium-loaded organic phase were separated. Then, the lithium-containing solution was successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation was carried out to obtain 139.63 g of lithium carbonate and 2.790 L of the mother liquor after lithium precipitation.

[0088] Among them, the composite extraction solution in this example includes dialkyldithiophosphinic acid, bis(diethyl dithiophosphate), 2-ethylhexyl phosphate mono-2-ethylhexyl ester and kerosene. The molar ratio of dialkyldithiophosphinic acid, bis(diethyl dithiophosphate), 2-ethylhexyl phosphate mono-2-ethylhexyl ester is 0.5:0.5:0.2, and the volume fraction of kerosene is 45%.

[0089] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation was 1.8 ppb, and the lithium content was 2.001 g / L.

[0090] The thallium-loaded organic phase was stripped with 5% hydrochloric acid at a volume ratio of 1:10 for 2 min to obtain a thallium-containing stripping solution and an empty composite extraction solution. The empty composite extraction solution was recycled to the extraction stage for continued use. After detection, the thallium content in the thallium-containing stripping solution was 234 ppm, and lithium was not detected.

[0091] Example 7

[0092] The difference between Example 7 and the reference example is that 0.4 L of the composite extraction solution was mixed with the leaching solution, shaken and extracted for 30 s, and then 3.2 L of the lithium-containing solution and 0.4 L of the thallium-loaded organic phase were separated. Then, the lithium-containing solution was successively subjected to impurity removal, purification, evaporation and concentration and other operations, and then lithium precipitation was carried out to obtain 139.78 g of lithium carbonate and 2.851 L of the mother liquor after lithium precipitation.

[0093] Among them, the composite extraction solution of this example includes 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphoric acid, 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, dibutyl dithiophosphate and kerosene. The molar ratio of 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphoric acid, 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, dibutyl dithiophosphate is 1:0.15:0.15, and the volume ratio of kerosene is 50%.

[0094] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation was 2.5 ppb, and the lithium content was 1.948 g / L.

[0095] The thallium-loaded organic phase was stripped with 10% hydrochloric acid at a volume ratio of 1:10 for 2 min to obtain a thallium-containing stripping solution and an empty composite extraction solution. The empty composite extraction solution was recycled to the extraction stage for continued use. After detection, the thallium content in the thallium-containing stripping solution was 294.1 ppm, and lithium was not detected.

[0096] Example 8

[0097] The difference between Example 8 and the reference example is that 0.32 L of the composite extraction solution was mixed with the leaching solution, shaken and extracted for 30 s, and then 3.2 L of the lithium-containing solution and 0.32 L of the thallium-loaded organic phase were separated. Then, the lithium-containing solution was successively subjected to impurity removal, purification, evaporation and concentration and other operations, and then lithium precipitation was carried out to obtain 139.83 g of lithium carbonate and 2.876 L of the mother liquor after lithium precipitation.

[0098] Among them, the composite extraction solution of this example includes dialkyldithiophosphinic acid, bis(2-ethylhexyl)dithiophosphoric acid, 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, trioctyl phosphate and kerosene. The molar ratio of dialkyldithiophosphinic acid, bis(2-ethylhexyl)dithiophosphoric acid, 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, trioctyl phosphate is 1:1:0.3:0.2, and the volume ratio of kerosene is 50%.

[0099] After analysis, the concentration of thallium ions in the mother liquor of lithium precipitation is 1.8 ppb, and the lithium content is 1.928 g / L.

[0100] The thallium-loaded organic phase is back-extracted with 10% hydrochloric acid at a volume ratio of 1:5 for 2 minutes to obtain a thallium-containing back-extraction solution and an empty composite extraction solution. The empty composite extraction solution is recycled to the extraction stage for continued use. After detection, the thallium content in the thallium-containing back-extraction solution is 184.1 ppm, and lithium is not detected.

[0101] Example 9

[0102] The flue gas generated by roasting is first passed through a dust removal device to remove particulate impurities, and then absorbed by a multi-stage water spray absorption tower to obtain 1 L of flue gas wastewater. The pH of the wastewater is 3, and the thallium concentration is 1021 ppb.

[0103] The difference between Example 9 and Example 1 is that the wastewater is combined with the leaching solution to obtain 4.2 L of mixed leaching solution, with a thallium content of about 3054 ppb and a lithium content of about 7.619 g / L. Then, 0.8 L of the composite extraction solution is mixed with the mixed leaching solution, and after shaking and extracting for 30 s, 4.2 L of lithium-containing solution and 0.8 L of thallium-loaded organic phase are separated. Then, the lithium-containing solution is successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation is carried out to obtain 138.08 g of lithium carbonate and 2.830 L of mother liquor of lithium precipitation.

[0104] After analysis, the concentration of thallium ions in the mother liquor of lithium precipitation is 2.0 ppb, and the lithium content is 2.076 g / L.

[0105] The thallium-loaded organic phase is back-extracted with 10% hydrochloric acid at a volume ratio of 1:5 for 2 minutes to obtain a thallium-containing back-extraction solution and an empty composite extraction solution. The empty composite extraction solution is recycled to the extraction stage for continued use. After detection, the thallium content in the thallium-containing back-extraction solution is 334.8 ppm, and lithium is not detected.

[0106] Example 10

[0107] The difference between Example 10 and Example 9 is that 1 L of the composite extraction solution of Example 2 is mixed with the mixed leaching solution, and after shaking and extracting for 30 s, 4.2 L of lithium-containing solution and 1 L of thallium-loaded organic phase are separated. Then, the lithium-containing solution is successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation is carried out to obtain 139.47 g of lithium carbonate and 2.792 L of mother liquor of lithium precipitation.

[0108] After analysis, the concentration of thallium ions in the mother liquor of lithium precipitation is 1.9 ppb, and the lithium content is 2.010 g / L.

[0109] The thallium-loaded organic phase was stripped with 10% hydrochloric acid at a volume ratio of 1:5 for 2 min to obtain a thallium-containing stripping solution and an empty composite extraction solution. The empty composite extraction solution was recycled to the extraction stage for continued use. After detection, the thallium content in the thallium-containing stripping solution was 268.5 ppm, and lithium was not detected.

[0110] Comparative Example 1

[0111] The difference between Comparative Example 1 and Example 1 is that the composite extraction solution includes 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid and kerosene, and the volume ratio of kerosene is 50%.

[0112] 0.6 L of the composite extraction solution was mixed with the leaching solution, and after shaking extraction for 2 min, 3.2 L of the lithium-containing solution and 0.6 L of the organic phase were separated. Then, the lithium-containing solution was successively subjected to impurity removal, purification, evaporation and concentration and other operations, and then lithium precipitation was carried out to obtain 139.92 g of lithium carbonate and 2.872 L of the mother liquor after lithium precipitation.

[0113] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation was 586 ppb, and the lithium content was 1.925 g / L.

[0114] The organic phase was stripped with 10% hydrochloric acid at a volume ratio of 1:5 for 2 min to obtain a stripping solution and an empty composite extraction solution. After detection, the thallium content in the stripping solution was 84.30 ppm, and lithium was not detected.

[0115] Comparative Example 2

[0116] The difference between Comparative Example 2 and Example 1 is that the composite extraction solution includes bis(2-ethylhexyl) phosphate and kerosene, and the volume ratio of kerosene is 50%.

[0117] 0.6 L of the composite extraction solution was mixed with the leaching solution, and after shaking extraction for 2 min, 3.2 L of the lithium-containing solution and 0.6 L of the organic phase were separated. Then, the lithium-containing solution was successively subjected to impurity removal, purification, evaporation and concentration and other operations, and then lithium precipitation was carried out to obtain 140.72 g of lithium carbonate and 2.837 L of the mother liquor after lithium precipitation.

[0118] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation was 4107 ppb, and the lithium content was 1.895 g / L.

[0119] The organic phase was stripped with 10% hydrochloric acid at a volume ratio of 1:5 for 2 min to obtain a stripping solution and an empty composite extraction solution. After detection, the thallium content in the stripping solution was 4.89 ppm, and lithium was not detected.

[0120] Comparative Example 3

[0121] The difference between Comparative Example 3 and Example 1 is that the composite extract includes 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphoric acid, di(2-ethylhexyl)phosphate and kerosene, the molar ratio of 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphoric acid to di(2-ethylhexyl)phosphate is 1:0.15, and the volume proportion of kerosene is 50%.

[0122] 0.6L of the composite extract was mixed with the leaching solution, and after oscillation extraction for 2 minutes, 3.2L of lithium-containing solution and 0.6L of organic phase were separated. The lithium-containing solution was then subjected to operations such as impurity removal, purification, evaporation and concentration to precipitate lithium, obtaining 140.52g of lithium carbonate and 2.795L of lithium precipitation mother liquor.

[0123] After analysis, the concentration of thallium ions in the lithium precipitation mother liquor was 342ppb and the lithium content was 1.937g / L.

[0124] The organic phase was stripped with 10% hydrochloric acid at a volume ratio of 1:5 for 2 minutes to obtain a stripping solution and an empty composite extract. The thallium content in the stripping solution was 90.35 ppm, and no lithium was detected.

[0125] Comparative Example 4

[0126] The difference between Comparative Example 4 and Example 1 is that the composite extract includes 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphoric acid, di(2-ethylhexyl)phosphate and kerosene, the molar ratio of 2,2'-methylene-bis(4,6-di-tert-butylphenyl)phosphoric acid to di(2-ethylhexyl)phosphate is 1:0.6, and the volume proportion of kerosene is 50%.

[0127] 0.6L of the composite extract was mixed with the leaching solution, and after oscillation extraction for 2 minutes, 3.2L of lithium-containing solution and 0.6L of organic phase were separated. The lithium-containing solution was then subjected to operations such as impurity removal, purification, evaporation and concentration to precipitate lithium, obtaining 138.34% lithium phosphate and 2.797L lithium precipitation mother liquor.

[0128] After analysis, the concentration of thallium ions in the lithium precipitation mother liquor was 325ppb and the lithium content was 2.083g / L.

[0129] The organic phase was stripped with 10% hydrochloric acid at a volume ratio of 1:5 for 2 minutes to obtain a stripping solution and an empty composite extract. The thallium content in the stripping solution was 90.59 ppm, and no lithium was detected.

[0130] Comparative Example 5

[0131] The difference between Comparative Example 5 and Example 1 is that the composite extraction solution comprises 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid, trihexylphosphine oxide and kerosene. The molar ratio of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid to trihexylphosphine oxide is 1:0.3, and the volume fraction of kerosene is 50%.

[0132] Take 0.6 L of the composite extraction solution and mix it with the leaching solution. After shaking and extracting for 2 min, separate 3.2 L of the lithium-containing solution and 0.6 L of the organic phase. Then, subject the lithium-containing solution to operations such as impurity removal, purification, evaporation and concentration in sequence, and then carry out lithium precipitation to obtain 140.62 g of lithium carbonate and 2.840 L of the mother liquor after lithium precipitation.

[0133] Upon analysis, the concentration of thallium ions in the mother liquor after lithium precipitation is 543 ppb, and the lithium content is 1.960 g / L.

[0134] Use 10% hydrochloric acid to strip the organic phase at a volume ratio of 1:5 for 2 min to obtain the stripping solution and the empty composite extraction solution. After detection, the thallium content in the stripping solution is 85.14 ppm, and no lithium is detected.

[0135] Comparative Example 6

[0136] The difference between Comparative Example 6 and Example 1 is that the composite extraction solution comprises 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and kerosene. The molar ratio of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid to 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione is 1:0.3, and the volume fraction of kerosene is 50%.

[0137] Take 0.6 L of the composite extraction solution and mix it with the leaching solution. After shaking and extracting for 2 min, separate 3.2 L of the lithium-containing solution and 0.6 L of the organic phase. Then, subject the lithium-containing solution to operations such as impurity removal, purification, evaporation and concentration in sequence, and then carry out lithium precipitation to obtain 139.31 g of lithium carbonate and 2.815 L of the mother liquor after lithium precipitation.

[0138] Upon analysis, the concentration of thallium ions in the mother liquor after lithium precipitation is 538 ppb, and the lithium content is 2.005 g / L.

[0139] Use 10% hydrochloric acid to strip the organic phase at a volume ratio of 1:5 for 2 min to obtain the stripping solution and the empty composite extraction solution. After detection, the thallium content in the stripping solution is 85.68 ppm, and the lithium content is 81 ppm.

[0140] Comparative Example 7

[0141] The difference between Comparative Example 7 and Example 1 is that the composite extraction solution includes 2,2'-methylene-bis(4,6-di-tert-butylphenyl) phosphoric acid, dimethyldi(N-octadecyl) ammonium chloride and kerosene. The molar ratio of 2,2'-methylene-bis(4,6-di-tert-butylphenyl) phosphoric acid to dimethyldi(N-octadecyl) ammonium chloride is 1:0.3, and the volume fraction of kerosene is 50%.

[0142] Take 0.6 L of the composite extraction solution and mix it with the leaching solution. After shaking and extracting for 2 min, separate 3.2 L of the lithium-containing solution and 0.6 L of the organic phase. Then, the lithium-containing solution is successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation is carried out to obtain 138.24 g of lithium carbonate and 2.784 L of the mother liquor after lithium precipitation.

[0143] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation is 650 ppb, and the lithium content is 2.100 g / L.

[0144] Use 10% hydrochloric acid to back-extract the organic phase with a volume ratio of 1:5 and a back-extraction time of 2 min to obtain the back-extraction solution and the empty composite extraction solution. After detection, the thallium content in the back-extraction solution is 83.22 ppm, and lithium is not detected.

[0145] Comparative Example 8

[0146] The difference between Comparative Example 8 and Example 1 is that the composite extraction solution includes 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, bis(2-ethylhexyl) phosphate and kerosene. The molar ratio of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione to bis(2-ethylhexyl) phosphate is 1:0.3, and the volume fraction of kerosene is 50%.

[0147] Take 0.6 L of the composite extraction solution and mix it with the leaching solution. After shaking and extracting for 2 min, separate 3.2 L of the lithium-containing solution and 0.6 L of the organic phase. Then, the lithium-containing solution is successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation is carried out to obtain 139.12 g of lithium carbonate and 2.790 L of the mother liquor after lithium precipitation.

[0148] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation is 4138 ppb, and the lithium content is 1.983 g / L.

[0149] Use 10% hydrochloric acid to back-extract the organic phase with a volume ratio of 1:5 and a back-extraction time of 2 min to obtain the back-extraction solution and the empty composite extraction solution. After detection, the thallium content in the back-extraction solution is 2.19 ppm, and the lithium content is 2468 ppm.

[0150] Comparative Example 9

[0151] The difference between Comparative Example 9 and Example 1 is that the composite extraction solution includes trihexylphosphine oxide, bis(2-ethylhexyl) phosphate, and kerosene. The molar ratio of trihexylphosphine oxide to bis(2-ethylhexyl) phosphate is 1:0.3, and the volume fraction of kerosene is 50%.

[0152] Take 0.6 L of the composite extraction solution and mix it with the leaching solution. After shaking and extracting for 2 min, separate 3.2 L of the lithium-containing solution and 0.6 L of the organic phase. Then, the lithium-containing solution is successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation is carried out to obtain 140.08 g of lithium carbonate and 2.756 L of the mother liquor after lithium precipitation.

[0153] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation is 4145 ppb, and the lithium content is 1.995 g / L.

[0154] Use 10% hydrochloric acid to back-extract the organic phase with a volume ratio of 1:5 and a back-extraction time of 2 min to obtain the back-extraction solution and the empty composite extraction solution. After detection, the thallium content in the back-extraction solution is 3.2 ppm, and lithium is not detected.

[0155] Comparative Example 10

[0156] The difference between Comparative Example 10 and Example 1 is that the composite extraction solution includes dimethyldi(N-octadecyl)ammonium chloride, bis(2-ethylhexyl) phosphate, and kerosene. The molar ratio of dimethyldi(N-octadecyl)ammonium chloride to bis(2-ethylhexyl) phosphate is 1:0.3, and the volume fraction of kerosene is 50%.

[0157] Take 0.6 L of the composite extraction solution and mix it with the leaching solution. After shaking and extracting for 2 min, separate 3.2 L of the lithium-containing solution and 0.6 L of the organic phase. Then, the lithium-containing solution is successively subjected to operations such as impurity removal, purification, evaporation and concentration, and then lithium precipitation is carried out to obtain 139.29 g of lithium carbonate and 2.846 L of the mother liquor after lithium precipitation.

[0158] After analysis, the concentration of thallium ions in the mother liquor after lithium precipitation is 4147 ppb, and the lithium content is 2.013 g / L.

[0159] Use 10% hydrochloric acid to back-extract the organic phase with a volume ratio of 1:5 and a back-extraction time of 2 min to obtain the back-extraction solution and the empty composite extraction solution. After detection, the thallium content in the back-extraction solution is 0.15 ppm, and lithium is not detected.

[0160] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered to be within the scope described in this specification.

[0161] The above-described embodiments merely represent several implementation manners of the present invention. The description thereof is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A method for separating lithium and thallium, characterized in that, It includes the following steps: Provide a stock solution containing lithium ions and thallium ions, wherein the stock solution is an acidic solution; Provide a composite extraction solution, the composite extraction solution includes an organic phosphoric acid, a phosphate ester and a diluent, and the molar ratio of the organic phosphoric acid to the phosphate ester is 1:0.2 - 1:0.

5. Use the composite extraction solution to extract the stock solution, and after phase separation, obtain a thallium-loaded organic phase and a lithium-containing solution. Prepare a lithium product from the lithium-containing solution; Perform back-extraction on the thallium-loaded organic phase, and after phase separation, obtain a thallium-containing solution and an unloaded composite extraction solution. Prepare a thallium product from the thallium-containing solution.

2. The method for separating lithium and thallium according to claim 1, characterized in that, The organic phosphoric acid is selected from at least one of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid, bis(2-ethylhexyl) phosphoric acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, dialkyldithiophosphinic acid, bis(2,4,4-trimethylpentyl) phosphinic acid, bis(diethyldithiophosphoric acid), di-n-butyldithiophosphoric acid, bis(2,4,4-trimethylpentyl) thiophosphoric acid, bis(2-ethylhexyl) dithiophosphoric acid.

3. The method for separating lithium and thallium according to claim 1, wherein The phosphate ester is selected from at least one of bis(2-ethylhexyl) phosphate ester, 2-ethylhexyl phosphate mono-2-ethylhexyl ester, dibutyl dithiophosphate, tricresyl phosphate, butyldiphenyl phosphate, trioctyl phosphate.

4. The method for separating lithium and thallium according to claim 1, wherein In the step of using the composite extraction solution to extract the stock solution, the molar ratio of the organic phosphoric acid in the composite extraction solution to the thallium ions in the stock solution is greater than or equal to 1.1:1; And / or, the temperature is from -5°C to 50°C.

5. The method for separating lithium and thallium according to any one of claims 1-4, characterized in that, The unloaded composite extraction solution is recycled for extracting the stock solution.

6. A method for extracting and preparing lithium products from lithium ore, characterized in that, It includes the following steps: Prepare an acidic leaching solution of lithium ore; Provide a composite extraction solution, the composite extraction solution includes an organic phosphoric acid, a phosphate ester and a diluent, and the molar ratio of the organic phosphoric acid to the phosphate ester is 1:0.2 - 1:0.

5. Use the composite extraction solution to extract the lithium ore leaching solution, and after phase separation, obtain a thallium-loaded organic phase and a lithium-containing solution; Prepare a lithium product from the lithium-containing solution.

7. The method for extracting and preparing lithium products from lithium ore according to claim 6, characterized in that, The organic phosphoric acid is selected from at least one of 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphoric acid, bis(2-ethylhexyl) phosphoric acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, dialkyldithiophosphinic acid, bis(2,4,4-trimethylpentyl) phosphinic acid, bis(diethyldithiophosphoric acid), di-n-butyldithiophosphoric acid, bis(2,4,4-trimethylpentyl) thiophosphoric acid, bis(2-ethylhexyl) dithiophosphoric acid.

8. The method for extracting and preparing lithium products from lithium ore according to claim 6, characterized in that, The phosphate ester is selected from at least one of bis(2-ethylhexyl) phosphate ester, 2-ethylhexyl phosphate mono-2-ethylhexyl ester, dibutyl dithiophosphate, tricresyl phosphate, butyldiphenyl phosphate, trioctyl phosphate.

9. The method for extracting and preparing lithium products from lithium ore according to claim 6, characterized in that, Prepare the lithium ore leaching solution by a roasting method, absorb the flue gas generated during the roasting process to obtain wastewater, and mix the wastewater into the lithium ore leaching solution.

10. The method for extracting and preparing lithium products from lithium ore according to any one of claims 6-9, characterized in that, In the step of extracting the lithium ore leaching solution with the described composite extraction solution, the molar ratio of the organic phosphoric acid in the composite extraction solution to the thallium ions in the lithium ore leaching solution is greater than or equal to 1.1:1; and / or, the temperature is from -5°C to 50°C.

11. The method for extracting and preparing lithium products from lithium ore according to any one of claims 6-9, characterized in that, The step further includes: stripping the thallium-loaded organic phase, separating phases to obtain a thallium-containing solution and the unloaded composite extraction solution, and recycling the unloaded composite extraction solution for extracting the lithium ore leaching solution.

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