Method for extracting lithium from high-calcium lithium-containing brine

Abstract

The invention discloses a method for extracting lithium from high-calcium lithium-containing brine, and belongs to the technical field of lithium ion enrichment and extraction of lithium-containing energy mineral products, the method for extracting lithium from high-calcium lithium-containing brine comprises the following steps: adding an aluminum-lithium layered hydroxide as a seed crystal and a sodium metaaluminate solution into original brine, and carrying out front-end lithium extraction. According to the method, a front-end lithium extraction mode is adopted, the sodium metaaluminate solution is directly added, conditions are controlled, and the aluminum-lithium layered hydroxide is used as the seed crystal, so that the lithium ions in the original brine are separated, and particularly, under the condition that the initial lithium ion concentration in the brine is relatively low, the separation rate of the lithium ions is remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of lithium ion enrichment and extraction of lithium-containing energy minerals, and particularly relates to a method for extracting lithium from high-calcium lithium-containing brine. Background Art

[0002] In recent years, with the rapid development of the new energy industry, the demand for lithium and its salts has gradually increased, and the sustainable development of lithium-containing mineral resources is an important direction in the current research of energy minerals.

[0003] Research shows that lithium resources in brine are relatively rich and the cost of lithium extraction is relatively low. Therefore, lithium extraction from brine has also received extensive attention and become a research hotspot. At present, the methods for extracting lithium from brine mainly include evaporation crystallization, precipitation method, extraction method, adsorption method and membrane separation method, and the main research object is brine with a high magnesium-lithium ratio. There is relatively little research on lithium extraction from brine with a high calcium-lithium ratio.

[0004] At present, in the technology for extracting lithium from high-calcium brine, Patent CN114014340A separates calcium and lithium in the brine by means of evaporation concentration - boron removal - multi-stage freezing calcium precipitation; Patent CN115927878A uses sodium sulfate to remove calcium to achieve calcium-lithium separation; Patent CN113061722A uses the extraction method to remove calcium; Patent CN114906864A uses the form of evaporation crystallization - combination of sodium hydroxide and sodium carbonate to remove calcium. The core idea of the technical solutions disclosed in the above patents is: brine → evaporation concentration and salt removal → boron removal → calcium and magnesium removal → lithium precipitation. This type of process usually places the lithium extraction process at the back end. The common problems are: when salts are precipitated during the evaporation process, Li ions are carried away in the form of mother liquor entrainment, resulting in a large loss of Li. Moreover, the calcium and magnesium contents in the concentrated brine increase, and the workload of calcium and magnesium removal is large. During the calcium and magnesium removal process, lithium will be lost with the precipitation entrainment, increasing the loss amount of Li, thus causing a decrease in the lithium recovery rate in the brine. Especially when the initial lithium ion concentration in the brine is low, the loss of lithium is more obvious. Summary of the Invention

[0005] In view of the above technical problems, the present invention proposes a method for extracting lithium from high-calcium lithium-containing brine; that is, by using the front-end lithium extraction method, the lithium ions in the raw brine are separated by directly adding sodium metaaluminate solution and controlling conditions.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A method for extracting lithium from high-calcium lithium-containing brine, comprising the following steps:

[0008] Adopt front-end lithium extraction, specifically: using aluminum-lithium layered hydroxide as a seed crystal, adding sodium metaaluminate solution to the raw brine for lithium extraction;

[0009] Among them, the chemical formula of the aluminum-lithium layered hydroxide is LiCl·2Al(OH)3·nH2O.

[0010] Optionally, the method for extracting lithium from high-calcium lithium-containing brine specifically includes the following steps:

[0011] Add the aluminum-lithium layered hydroxide and sodium metaaluminate solution to the raw brine, adjust the pH, and then carry out stirring reaction, filtration, and washing in sequence; among them, the solid phase is dried to a constant weight to obtain the 1# solid phase, and the liquid phase is the 1# brine for standby;

[0012] Wash, oscillate, and filter the 1# solid phase, and the obtained solid phase is dried to a constant weight to obtain the 2# solid phase; the filtrate is the 1# filtrate for standby;

[0013] Evaporate and concentrate the 1# filtrate, and then add it to the sodium carbonate solution for precipitation reaction to obtain Li2CO3;

[0014] Carry out a heating reaction on the 2# solid phase and the NaOH solution, and the filtered solid phase is recorded as the 3# solid phase, and the filtrate is recorded as the 2# filtrate for standby;

[0015] Add sodium metaaluminate to the 2# filtrate for recycling as the reaction solution.

[0016] Optionally, the preparation process of the sodium metaaluminate solution is as follows:

[0017] Mix sodium metaaluminate and water according to a dosage ratio of (0.3 g - 1.0 g)∶1 mL, stir at 100 - 150 °C until fully dissolved, and then cool to room temperature for standby.

[0018] Optionally, the dosage ratio of the sodium metaaluminate solution, aluminum-lithium layered hydroxide, and raw brine is 7 - 20 mL∶0.1 g - 0.5 g∶1000 mL.

[0019] Optionally, the pH is 7.5 - 8.5.

[0020] Optionally, the stirring reaction time is 4 - 8 h.

[0021] Optionally, the dosage ratio of the 1# solid phase to deionized water is 1 g∶20 - 40 mL.

[0022] Optionally, the concentration of the NaOH solution is 0.02 - 0.1 g / mL.

[0023] Optionally, the heating reaction conditions are: stirring reaction at 100 - 150 °C for 6 - 12 h.

[0024] Optionally, the mass concentration ratio of calcium to lithium in the raw brine is (4000 - 5000)∶(60 - 90).

[0025] Compared with the prior art, the present invention has the following advantages and technical effects:

[0026] The present invention adopts the method of extracting lithium at the front end. By directly adding sodium metaaluminate solution, controlling conditions, and synergistically using lithium-aluminum layered hydroxide as a seed crystal, the separation of lithium ions in the raw brine is achieved; especially in the case where the initial lithium ion concentration in the brine is relatively low, the separation rate of lithium ions is significantly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0028] Figure 1 is the process flow chart of the lithium extraction method of the present invention;

[0029] Figure 2 is the reaction equation involved in steps 2-5 of the present invention;

[0030] Figure 3 is the XRD pattern of 1# solid phase (a) in step 2 and the Li2CO3 prepared in step 4 and commercial Li2CO3 (b) in Example 1 of the present invention;

[0031] Figure 4 is the SEM spectrum of the Li2CO3 prepared in step 4 of Example 1 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0032] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation to the present invention, but rather as a more detailed description of certain aspects, characteristics, and implementation embodiments of the present invention.

[0033] It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0034] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although this invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of this invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to those documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0035] Without departing from the scope or spirit of this invention, various modifications and variations can be made to the specific embodiments of the specification of this invention, which are obvious to those skilled in the art. Other embodiments obtained from the specification of this invention are obvious to those skilled in the art. The specification and examples of this invention are merely exemplary.

[0036] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0037] As Figure 1 shown, an embodiment of this invention discloses a method for extracting lithium from high-calcium lithium-containing brine, which includes the following steps:

[0038] Step 1: Mix sodium metaaluminate and water according to a dosage ratio of (0.3 g - 1.0 g)∶1 mL, stir at 100 - 150 °C until fully dissolved, and then cool to room temperature for standby;

[0039] Prepare lithium-aluminum layered hydroxide by the coprecipitation method, and the specific preparation process is as follows:

[0040] Fully dissolve 26.6 g of AlCl3 and 4.0 g of LiCl in 200 mL of distilled water to obtain a mixed solution. Under stirring conditions, slowly add a NaOH solution with a concentration of 1 mol / L to the above mixed solution, adjust the pH to 7.0 - 7.5, continue stirring and reacting for 6 h, then filter, wash, and dry to prepare lithium-aluminum layered hydroxide (LiCl·2Al(OH)3·nH2O) for standby.

[0041] Step 2: Add the sodium metaaluminate solution and lithium-aluminum layered hydroxide in Step 1 to 1000 mL of raw brine at the same time, and adjust the pH within the range of 7.5 - 8.5, stir and react at room temperature for 4 - 8 h, then perform vacuum filtration and washing. The solid phase is dried to constant weight at 60 °C, denoted as the 1# solid phase, and the liquid phase is denoted as the 1# brine for standby;

[0042] Among them, the volume ratio of the sodium metaaluminate solution to the raw brine is 7 - 20 mL∶1000 mL;

[0043] The dosage ratio of aluminum-lithium layered hydroxide to raw brine is 0.1 g - 0.5 g∶1000 mL.

[0044] Step 3: Mix the solid phase #1 with deionized water in a certain ratio, shake for 6 - 12 h, dry the filtered solid phase at 60 °C to constant weight, denote it as the solid phase #2, and reserve the filtrate as the filtrate #1 for later use;

[0045] The ratio of the solid phase #1 to deionized water is 1 g∶20 - 40 mL;

[0046] Step 4: After evaporating and concentrating the filtrate #1, add it to the sodium carbonate solution, and obtain the Li2CO3 product after the precipitation reaction.

[0047] Step 5: Stir and react the solid phase #2 and 5 - 20 mL of NaOH solution at 100 - 150 °C for 6 - 12 h, denote the filtered solid phase as the solid phase #3, and reserve the filtrate as the filtrate #2 for later use;

[0048] Among them, the concentration of the NaOH solution is 0.02 - 0.1 g / mL;

[0049] Step 6: Supplement sodium aluminate in the filtrate #2, return it to Step 1, and recycle it as the reaction solution.

[0050] During the lithium extraction method of the present invention, the concentrations of Na + , K + , Ca 2+ , Mg 2+ , Li + in the involved liquids are all detected by ICP - OES.

[0051] Figure 2 For the reactions involved in Steps 2 - 5 of the present invention, the equations are not chemically balanced and are only used to describe the main reaction processes involved in this technology. Specifically, during the lithium extraction process of the present invention, the reaction principle involved is:

[0052] The purpose of dissolving sodium aluminate at high temperature and cooling to room temperature in Step 1 is to form a supersaturated solution of sodium aluminate, and at the same time prepare aluminum-lithium layered hydroxide (LiCl·2Al(OH)3·nH2O) as a seed crystal (used to induce the formation of aluminum-lithium layered hydroxide and improve its formation efficiency) for reaction with the brine in Step 2;

[0053] After mixing and reacting the raw brine and sodium aluminate solution in Step 2 and filtering, the obtained brine #1 is a brine mainly composed of Na + and K + , and contains a certain amount of Ca 2+ and Mg 2+ . From Figure 3It can be seen from the XRD spectrum that the solid phase of 1# is a mixture of hydrocalumite, magnesium aluminum hydrotalcite, LiCl·2Al(OH)3·nH2O, Al(OH)3 and Mg(OH)2. It can be seen that this step separates a part of Ca in the brine 2+ , most of Mg 2+ and most of Li + from the brine in the form of insoluble substances.

[0054] In step 3, washing with water elutes Li + in the lithium aluminum layered hydroxide into the liquid phase, that is, obtaining the filtrate of 1# (the elution process is as shown in Figure 2 the reaction formula of step 3). However, hydrocalumite, magnesium aluminum hydrotalcite, Al(OH)3 and Mg(OH)2 are all insoluble in water. Thus, Li + is separately separated from the solid phase of 1# in this way, and the remaining solid phase is the solid phase of 2#, whose main components are hydrocalumite, magnesium aluminum hydrotalcite, (1-x)LiCl·2Al(OH)3·nH2O, Al(OH)3 and Mg(OH)2. Subsequently, Li2CO3 is prepared through step 4.

[0055] Step 5 is to dissolve (1-x)LiCl·2Al(OH)3·nH2O and Al(OH)3 with alkali to convert them into sodium aluminate solution, and return it to step 1 for recycling by supplementing sodium aluminate. The remaining solid phase of 3# mainly consists of hydrocalumite, magnesium aluminum hydrotalcite and Mg(OH)2.

[0056] In summary, the core of the present invention lies in adopting the method of separating Li + at the front end, which can not only effectively separate Li + in the original brine, and the loss of Li + is small; in addition, the reagents used in the present invention are simple, safe and environmentally friendly, and the recycling of sodium aluminate is realized to a certain extent.

[0057] In the present invention, "room temperature" refers to 20-30°C unless otherwise specified.

[0058] All raw materials used in the present invention are obtained by purchasing in the market. Commercial Li2CO3 is purchased from Shanghai Macklin Biochemical Co., Ltd.; the main cation compositions of the brines used in the examples and comparative examples of the present invention are shown in Table 1.

[0059] Table 1 Main cation components and concentrations in the brine

[0060]

[0061] The technical solution of the present invention will be further described below through examples.

[0062] Example 1

[0063] A method for extracting lithium from high-calcium lithium-containing brine, comprising the following steps:

[0064] Step 1: Mix sodium metaaluminate and water in a ratio of 0.6 g∶1 mL, stir at 130 °C until fully dissolved, and then cool to room temperature for standby; at the same time, prepare lithium-aluminum layered hydroxide by coprecipitation method for standby;

[0065] Step 2: Add 10 mL of the sodium metaaluminate solution in Step 1 and 0.4 g of lithium-aluminum layered hydroxide to 1000 mL of raw brine, adjust the pH to 8.0, stir and react at room temperature for 6 h, perform vacuum filtration and washing, and then dry the solid phase at 60 °C to constant weight, denoted as Solid Phase 1#, and the liquid phase is denoted as Brine 1# for standby;

[0066] Step 3: Mix Solid Phase 1# with deionized water in a ratio of 1 g∶20 mL, oscillate for 12 h, dry the filtered solid phase at 60 °C to constant weight, denoted as Solid Phase 2#, and the filtrate is denoted as Filtrate 1# for standby;

[0067] Step 4: After evaporating and concentrating Filtrate 1#, add saturated sodium carbonate solution, and after the precipitation reaction, wash the solid phase and dry it to obtain Li2CO3 product;

[0068] Step 5: Stir and react Solid Phase 2# and 10 mL of 0.04 g / mL NaOH solution at 130 °C for 8 h, and the filtered solid phase is denoted as Solid Phase 3#, and the filtrate is denoted as Filtrate 2# for standby;

[0069] Step 6: Supplement sodium metaaluminate in Filtrate 2# and return it to Step 1 for recycling as the reaction solution.

[0070] Figure 3 XRD patterns of Solid Phase 1# (a) in Step 2 of Example 1 of the present invention, Li2CO3 prepared in Step 4, and commercial Li2CO3 (b); from Figure 3 the XRD spectrum, it can be seen that Solid Phase 1# is a mixture of hydrocalumite, magnesium aluminum hydrotalcite, lithium-aluminum layered hydroxide (LiCl·2Al(OH)3·nH2O), Al(OH)3, and Mg(OH)2. In this step, Ca 2+ , Mg 2+ and Li + in the brine are separated from the brine in the form of insoluble substances.

[0071] Figure 4 SEM spectrum of Li2CO3 prepared in Step 4 of Example 1 of the present invention.

[0072] Example 2

[0073] A method for extracting lithium from high-calcium lithium-containing brine, comprising the following steps:

[0074] Step 1: Mix sodium aluminate and water in a ratio of 0.4 g∶1 mL, stir at 140 °C until fully dissolved, then cool to room temperature for later use; simultaneously, prepare lithium-aluminum layered hydroxide by co-precipitation method for later use;

[0075] Step 2: Add 15 mL of the sodium aluminate solution from Step 1 and 0.2 g of lithium-aluminum layered hydroxide to 1000 mL of raw brine, adjust the pH to 7.5, stir and react at room temperature for 5 h, perform vacuum filtration and washing, then dry the solid phase at 60 °C to constant weight, denoted as 1# solid phase, and the liquid phase is denoted as 1# brine for later use;

[0076] Step 3: Mix 1# solid phase and deionized water in a ratio of 1 g∶30 mL, oscillate for 8 h, dry the filtered solid phase at 60 °C to constant weight, denoted as 2# solid phase, and the filtrate is denoted as 1# filtrate for later use;

[0077] Step 4: After evaporating and concentrating 1# filtrate, add it to sodium carbonate solution, and after precipitation reaction, wash and dry the solid phase to obtain Li2CO3 product;

[0078] Step 5: Stir and react 2# solid phase and 15 mL of 0.03 g / mL NaOH solution at 140 °C for 10 h, the filtered solid phase is denoted as 3# solid phase, and the filtrate is denoted as 2# filtrate for later use;

[0079] Step 6: Supplement sodium aluminate in 2# filtrate and return it to Step 1 as reaction solution for recycling.

[0080] Example 3

[0081] A method for extracting lithium from high-calcium lithium-containing brine, comprising the following steps:

[0082] Step 1: Mix sodium aluminate and water in a ratio of 0.30 g∶1 mL, stir at 110 °C until fully dissolved, then cool to room temperature for later use; simultaneously, prepare lithium-aluminum layered hydroxide by co-precipitation method for later use;

[0083] Step 2: Add 20 mL of the sodium aluminate solution from Step 1 and 0.3 g of lithium-aluminum layered hydroxide to 1000 mL of raw brine, control the pH to 8.0, stir and react at room temperature for 8 h, perform vacuum filtration and washing, then dry the solid phase at 60 °C to constant weight, denoted as 1# solid phase, and the liquid phase is denoted as 1# brine for later use;

[0084] Step 3: Mix 1# solid phase and deionized water in a ratio of 1 g∶40 mL, oscillate for 6 h, dry the filtered solid phase at 60 °C to constant weight, denoted as 2# solid phase, and the filtrate is denoted as 1# filtrate for later use;

[0085] Step 4: After evaporating and concentrating 1# filtrate, add it to sodium carbonate solution, and after precipitation reaction, wash and dry the solid phase to obtain Li2CO3 product;

[0086] Step 5: Stir and react the 2# solid phase and 20 mL of 0.02 g / mL NaOH solution at 110 °C for 6 h. The solid phase after filtration is denoted as the 3# solid phase, and the filtrate is denoted as the 2# filtrate for standby.

[0087] Step 6: Supplement sodium aluminate to the 2# filtrate and return it to Step 1 for recycling as the reaction solution.

[0088] Example 4

[0089] A method for extracting lithium from high-calcium lithium-containing brine, comprising the following steps:

[0090] Step 1: Mix sodium aluminate and water in a ratio of 0.7 g:1 mL, stir at 120 °C until fully dissolved, and then cool to room temperature for standby; at the same time, prepare lithium-aluminum layered hydroxide by coprecipitation method for standby.

[0091] Step 2: Add 8 mL of 0.6 g / mL sodium aluminate solution and 0.5 g of lithium-aluminum layered hydroxide to 1000 mL of raw brine, control the pH = 8.5, stir and react at room temperature for 4 h, perform vacuum filtration and washing, and then dry the solid phase at 60 °C to constant weight, denoted as the 1# solid phase, and the liquid phase is denoted as the 1# brine for standby.

[0092] Step 3: Mix the 1# solid phase and deionized water in a ratio of 1 g:35 mL, shake for 9 h, dry the solid phase after filtration at 60 °C to constant weight, denoted as the 2# solid phase, and the filtrate is denoted as the 1# filtrate for standby.

[0093] Step 4: After evaporating and concentrating the 1# filtrate, add it to the sodium carbonate solution, and after precipitation reaction, wash and dry the solid phase to obtain Li2CO3 product.

[0094] Step 5: Stir and react the 2# solid phase and 8 mL of 0.07 g / mL NaOH solution at 120 °C for 8 h. The solid phase after filtration is denoted as the 3# solid phase, and the filtrate is denoted as the 2# filtrate for standby.

[0095] Step 6: Supplement sodium aluminate to the 2# filtrate and return it to Step 1 for recycling as the reaction solution.

[0096] Comparative Example 1

[0097] The difference from Example 1 is that the addition amount of sodium aluminate solution in Step 2 is adjusted to 6 mL, and other steps and conditions are the same as those in Example 1.

[0098] Comparative Example 2

[0099] The difference from Example 1 is that the reaction time in Step 2 is adjusted to 2 h, and other steps and conditions are the same as those in Example 1.

[0100] Comparative Example 3

[0101] It is different from Example 1 in that the pH in Step 2 is controlled to 10, and other steps and conditions are the same as those in Example 1.

[0102] Comparative Example 4

[0103] It is different from Example 1 in that no lithium-aluminum layered hydroxide is added in Step 2, and other steps and conditions are the same as those in Example 1.

[0104] Effect Verification

[0105] In Examples 1-4 and Comparative Examples 1-4, the concentrations (mg / L) and separation rates of Li + , Ca 2+ and Mg 2+ in the No. 1 brine in Step 2 are shown in Table 2.

[0106] Table 2

[0107]

[0108]

[0109] Comparing the methods used in Examples 1-4 and Comparative Examples 1-4 of the present invention, it can be seen from the lithium ion separation rate that the methods of Examples 1-4 show significant effects in the separation efficiency of lithium ions at the front end, reaching 92.6%-97.6%. This indicates that the lithium extraction method that defines the reaction conditions in Step 2 and uses lithium-aluminum layered hydroxide as a seed has good selectivity and high separation ability for lithium.

[0110] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A method for extracting lithium from high-calcium lithium-containing brine, characterized in that, It includes the following steps: Using lithium aluminum layered hydroxide as a seed crystal, adding sodium aluminate solution to the raw brine for front-end lithium extraction.

2. The method for extracting lithium from high-calcium lithium-containing brine according to claim 1, wherein Specifically, it includes the following steps: Adding lithium aluminum layered hydroxide and sodium aluminate solution to the raw brine, adjusting the pH, and then successively carrying out stirring reaction, filtration, and washing; among them, the solid phase is dried to a constant weight to obtain the 1# solid phase; the liquid phase is the 1# brine for standby; Washing, oscillating, and filtering the 1# solid phase, and the obtained solid phase is dried to a constant weight to obtain the 2# solid phase; the filtrate is the 1# filtrate for standby; Evaporating and concentrating the 1# filtrate, and then adding it to sodium carbonate solution for precipitation reaction to obtain Li2CO3.

3. A method for extracting lithium from high-calcium lithium-containing brine according to claim 2, characterized in that, The preparation process of the sodium aluminate solution is as follows: Mixing sodium aluminate and water according to a dosage ratio of (0.3 g - 1.0 g)∶1 mL, stirring and fully dissolving at 100 - 150 °C, and cooling to room temperature.

4. A method for extracting lithium from high-calcium lithium-containing brine according to claim 2, characterized in that, The dosage ratio of the sodium aluminate solution, lithium aluminum layered hydroxide, and raw brine is 7 - 20 mL∶0.1 g - 0.5 g∶1000 mL.

5. A method for extracting lithium from high-calcium lithium-containing brine according to claim 2, characterized in that, The pH is 7.5 - 8.

5.

6. A method for extracting lithium from high-calcium lithium-containing brine according to claim 2, characterized in that, The time of the stirring reaction is 4 - 8 h.

7. A method for extracting lithium from high-calcium lithium-containing brine according to claim 2, characterized in that, The dosage ratio of the 1# solid phase to water is 1 g∶20 - 40 mL.

8. A method for extracting lithium from high-calcium lithium-containing brine according to claim 1, characterized in that, The mass concentration ratio of calcium to lithium in the raw brine is (4000 - 5000)∶(60 - 90).

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