CN117248123A - Method for directly extracting lithium from lithium-containing brine with low calcium and magnesium content - Google Patents

Method for directly extracting lithium from lithium-containing brine with low calcium and magnesium content Download PDF

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Publication number
CN117248123A
CN117248123A CN202311257813.4A CN202311257813A CN117248123A CN 117248123 A CN117248123 A CN 117248123A CN 202311257813 A CN202311257813 A CN 202311257813A CN 117248123 A CN117248123 A CN 117248123A
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China
Prior art keywords
lithium
magnesium
calcium
brine
low
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Pending
Application number
CN202311257813.4A
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Chinese (zh)
Inventor
曲昊
张健
霍东云
方磊
张模涛
洪明
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Zhejiang Hengli New Energy Co ltd
Institute of Process Engineering of CAS
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Zhejiang Hengli New Energy Co ltd
Institute of Process Engineering of CAS
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Priority to CN202311257813.4A priority Critical patent/CN117248123A/en
Publication of CN117248123A publication Critical patent/CN117248123A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Abstract

The invention provides a method for directly extracting lithium from lithium-containing brine with low calcium and magnesium, which comprises the following steps: s1: adding a calcium magnesium ion sequestering agent to the low calcium magnesium lithium-containing brine to stabilize the calcium magnesium in the brine in a high pH environment without forming a precipitate; s2: mixing low-calcium-magnesium lithium-containing brine added with a calcium-magnesium ion masking agent with an extraction system, and adjusting the pH to be more than 9 to extract lithium in an alkaline environment; s3: mixing the extraction system loaded with lithium with a stripping agent, and adjusting the pH value to be less than 8 to carry out stripping of lithium; wherein, in the lithium-containing brine with low calcium and magnesium, 0g/L < Ca <1g/L,0g/L < Mg <1g/L; wherein the calcium-magnesium ion masking agent is a chelating agent.

Description

Method for directly extracting lithium from lithium-containing brine with low calcium and magnesium content
Technical Field
The invention relates to the technical field of lithium extraction, in particular to a method for directly extracting lithium from lithium-containing brine with low calcium and magnesium content.
Background
For salt lake brine with low calcium and magnesium, the pH is generally above 7, and the prior art needs to remove the calcium and magnesium before adding an extractant for extraction, usually adding alkali for removal in a form of precipitation. Therefore, when the calcium lithium or magnesium lithium in the salt lake brine with low calcium and magnesium is higher, a large amount of alkaline residues can be generated per ton of lithium carbonate produced, so that the environment is polluted and the production cost is increased.
Disclosure of Invention
The invention aims to provide a method for directly extracting lithium from lithium-containing brine with low calcium and magnesium without removing calcium and magnesium firstly.
In order to solve the technical problems, the method for directly extracting lithium from lithium-containing brine with low calcium and magnesium provided by the invention comprises the following steps:
s1: adding a calcium magnesium ion masking agent to the low calcium magnesium containing lithium brine to stabilize the calcium magnesium in the brine without forming a precipitate;
s2: mixing low-calcium-magnesium lithium-containing brine added with a calcium-magnesium ion masking agent with an extraction system, and adjusting the pH to be more than 9 to extract lithium in an alkaline environment;
s3: mixing the extraction system loaded with lithium with a stripping agent, and adjusting the pH value to be less than 8 to carry out stripping of lithium;
wherein, in the lithium-containing brine with low calcium and magnesium, 0g/L < Ca <1g/L,0g/L < Mg <1g/L;
wherein the calcium-magnesium ion masking agent is a chelating agent.
Alternatively, in step S2, 9< ph <14, preferably 10< ph <13.
Alternatively, in step S3, the pH may be less than 8, preferably 7< pH <7.5.
Optionally, the calcium magnesium ion masking agent comprises any one or any combination of two or more of EDTA (ethylenediamine tetraacetic acid), EGTA (ethylenediamine tetraacetic acid), BAPTA (1, 2-bis (aminomethyl) benzodiphenol), CDTA (cyclohexylimine tetraacetic acid), HEDTA (ethylenediamine tetraacetic acid N hydroxyethyl trimethylamine), potassium sodium tartrate, and trisodium nitrilotriacetate.
Optionally, li is more than or equal to 0.2g/L in the lithium-containing brine with low calcium and magnesium, and anions comprise Cl - 、SO 4 2- And CO 3 2- Any one or any combination of two or more of them.
Optionally, the extraction system is a composite extraction system, and the composite extraction system comprises a chelating extractant, a neutral extractant and a diluent;
wherein the neutral extractant is neutral phosphine which contains any one or a combination of at least two of tributyl phosphate TBP, dimethyl heptyl methyl phosphate P350, trioctylphosphine oxide TOPO, trioctyl/hexyl phosphine oxide Cyanex923 or N, N di- (1-methylheptyl) acetamide N503;
wherein the chelating extractant comprises any one or at least two of 2-hydroxy-5-nonylacetophenone oxime LIX84, dodecylphenyl-methyl-beta-diketone LIX54, 2-hydroxy-5-nonylbenzaldehyde oxime LIX860 and extractant with same diketone functional group.
Optionally, the volume ratio of neutral extractant to chelating extractant is (0.2-2): 1, preferably (1-2): 1, more preferably 1:1.
optionally, in step S2, the pH is adjusted by using a pH adjuster, where the pH adjuster is an inorganic salt of sodium or an inorganic salt of potassium. Can be NaOH or Na 2 CO 3 、KOH、K 2 CO 3 Etc
Optionally, the calcium-magnesium ion masking agent accounts for 0.01-0.1% of the volume ratio of the lithium-containing brine of the low calcium and magnesium. Wherein, the calcium-magnesium ion masking agent does not need to be excessive and trace calcium-magnesium residues can be completed. In other embodiments, the calcium magnesium ion masking agent may also be in excess, but at a corresponding increase in cost of use.
Optionally, during back extraction in step S3, the ratio of the volume of the organic phase to the volume of the aqueous phase is 20:1-1:2.
Optionally, in step S2, the ratio of the volume of the organic phase to the volume of the aqueous phase is 1:2 to 1:10. Wherein the ratio of the organic phase to the aqueous phase in the steps S3 and S2 is adjusted according to the concentration of lithium.
Alternatively, the diluent may be a liquid-phase diluent such as alcohols, ethers, water, coal oil, etc., and the kind of the diluent is not limited in the present application as long as it can serve as a dilution chelate and neutral phosphine.
Optionally, the stripping agent can be inorganic acid such as hydrochloric acid, sulfuric acid, etc. or CO 2 、SO 2 And (3) continuously introducing the acid gas. In the S3 step, CO can be directly introduced 2 Or SO 2 The pH of the acid gas stripping agent can be directly adjusted by directly passing through an inorganic acid stripping agent such as hydrochloric acid, sulfuric acid and the like.
Alternatively, the apparatus for effecting extraction-stripping may be a box-type extraction tank, an extraction column or a centrifugal extractor.
Alternatively, the number of extraction-stripping stages may be 1 or more, with the multistage extraction/stripping being performed in countercurrent.
Because the person skilled in the art falls into the thinking of ' adding alkali or carbonate to calcium and magnesium for removal in an alkaline extraction environment to extract the brine ' in order to improve the extraction rate and the product purity of lithium ', the invention breaks through the thinking, and before extraction, calcium and magnesium are firstly stabilized in the brine by using a calcium and magnesium ion masking agent, lithium is extracted in an alkaline environment, particularly at high pH, but calcium and magnesium cannot precipitate out, the total yield of finally extracted lithium is more than 75%, even more than 90%, the purity of a lithium carbonate product can also be more than 89%, even more than 99%, the running cost is low, the investment is small, and the method has obvious technical advantages.
Especially when the volume ratio of the neutral extractant to the chelating extractant is (1-2): 1, the yield reaches more than 90% when the extraction process is proper.
Furthermore, the compound extraction system comprises a chelating extractant, and the chelating extractant can chelate calcium and magnesium without being extracted, thereby greatly increasing the efficiency of extracting lithium and the purity of products.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
S01: EDTA was added to brine (Li 0.2g/L, mg 0.5g/L, ca 0.1 g/L) at a ratio of 0.05% by volume, and mixed well.
S02: adopting a compound extraction system with the volume ratio of 20 percent of chelating extractant (2-hydroxy-5-nonylacetophenone oxime), 20 percent of neutral phosphine (tributyl phosphate) and 60 percent of diluent (kerosene), extracting three stages after adjusting pH=11 in the volume ratio of organic phase to water phase of O/A=5:1,
s03: introducing CO under the condition of clean water and loaded organic phase=1:6 2 Gas pH adjustment<8, carrying out single-stage back extraction to obtain lithium bicarbonate solution with the lithium concentration of 5.7g/L, and heating to 80 ℃ to obtain a lithium carbonate product, wherein the total yield of Li is 95%, and the purity of the lithium carbonate product is 99%.
Example 2
Example 2 differs from example 1 in that the volume ratio of EDTA in step S01 is 0.01%, the total yield of Li is 95%, and the purity of the lithium carbonate product is 96.5%.
Example 3
Example 3 is different from example 1 in that the volume ratio of EDTA in step S01 is 1%, the total yield of Li is 96%, and the purity of the lithium carbonate product is 99.6%.
Example 4
Example 4 differs from example 1 in that in the brine used, li 0.2g/L, mg 0.9g/L and Ca 0.9g/L are used. The total yield of Li was 91% and the purity of the lithium carbonate product was 89%.
Example 5
Example 5 differs from example 1 in that in the brine used, li 0.2g/L, mg 0.1g/L, ca 0.1g/L are used. The total yield of Li was 99% and the purity of the lithium carbonate product was 99.7%.
Example 6
Example 6 differs from example 1 in that in step S02 the pH is adjusted to pH >8.2, the total yield of li is 80%, the purity of the lithium carbonate product is 92%.
Example 7
Example 7 differs from example 1 in that the calcium magnesium ion masking agent used in step S01 is ethylenediamine tetraacetic acid N-hydroxyethyl trimethylamine, the total yield of Li is 94% and the purity of the lithium carbonate product is 99.3%.
Example 8
Example 8 differs from example 7 in that the chelating extractant in step S02 is dodecylphenyl-methyl- β -diketone with a total yield of Li of 95.6% and a purity of 99.2% for the lithium carbonate product.
Example 9
Example 9 differs from example 1 in that the combined extraction system is 40% chelating extractant and 20% neutral phosphine and 40% diluent by volume, the total yield of Li is 98% and the purity of the lithium carbonate product is 99.5%.
Example 10
Example 10 differs from example 1 in that the combined extraction system is composed of 4% chelating extractant, 20% neutral phosphine and 76% diluent by volume, the total yield of Li being 60% and the purity of the lithium carbonate product being 98%.
Example 11
Example 11 differs from example 1 in that the ratio of the volume of the organic phase to the volume of the aqueous phase during the stripping in step S3 is 2: the total yield of Li was 98.5% and the purity of the lithium carbonate product was 99.1%.
Example 12
Example 12 differs from example 1 in that in step S2 the ratio of the volume of the organic phase to the volume of the aqueous phase is 10:1. the total yield of Li was 75% and the purity of the lithium carbonate product was 99.2%.
Example 13
Example 13 differs from example 1 in that the calcium-magnesium ion masking agent used in step S01 of example 13 was a mixture of EDTA and ethylenediamine tetraacetic acid N-hydroxyethyl trimethylamine in an amount of 0.05% (by volume), the total yield of Li was 95%, and the purity of the lithium carbonate product was 99.2%.
Comparative example 1
Comparative example 1 differs from example 1 in that step S01 and step S02 are performed simultaneously, i.e., comprising:
s01': adding EDTA in an amount of 0.05% (volume ratio) into brine (Li 0.2g/L, mg 0.5g/L and Ca 0.1 g/L), simultaneously adding a compound extraction system of 20% chelating extractant, 20% neutral phosphine and 60% diluent, and extracting three stages after adjusting pH=11 at the volume ratio of organic phase to aqueous phase of O/A=5:1;
s02': introducing CO under the condition of clean water and loaded organic phase=1:6 2 Gas pH adjustment<8, carrying out single-stage back extraction to obtain lithium bicarbonate solution with the lithium concentration of 5.7g/L, and heating to 80 ℃ to obtain a lithium carbonate product, wherein the total yield of Li is 40%, and the purity of the lithium carbonate product is 70%.
Comparative example 2
Comparative example 2 differs from example 1 in that the complex extraction system does not contain chelating extractant. I.e. the complex extraction system in step S02 is 20% chelating extractant and 60% diluent.
The total yield of Li was 12% and the purity of the lithium carbonate product was 20%.
Comparative example 3
Comparative example 3 differs from example 1 in that the chelation was performed using an alkali solution added to remove calcium and magnesium instead of the chelating agent in S01 of comparative example 3.
S01: naOH solution was added to brine (Li 0.2g/L, mg 0.5g/L, ca 0.1 g/L), and then filtered to precipitate, and the pH was controlled at 11-13 throughout the reaction.
S02: three stages of extraction were performed using a complex extraction system of 20% chelating extractant and 20% neutral phosphine and 60% diluent at an organic to aqueous phase volume ratio O/a=5:1.
S03: introducing CO under the condition of clean water and loaded organic phase=1:6 2 Gas pH adjustment<8, carrying out single-stage back extraction to obtain lithium bicarbonate solution with the lithium concentration of 5.7g/L, and heating to 80 ℃ to obtain a lithium carbonate product, wherein the total yield of Li is 95%, and the purity of the lithium carbonate product is 92%.
In summary, by comparing the data of comparative examples 1 and 2 with the data of examples 1-13 of the present application, it is known that by stabilizing calcium and magnesium in brine with a calcium and magnesium ion masking agent prior to extraction, the overall yield and product purity of the final extracted lithium are significantly improved. The purity of the product of example 13 is improved over that of example 1.
Although the total yield and the product purity finally obtained in comparative example 3 are close to the effects of the scheme in the present application, the step of removing the residues is not performed in comparative example 3, and the scheme of comparative example 3 requires an additional process step in the actual production process, the process is troublesome, the cost is high, a large amount of alkaline residues are generated to pollute the environment, and the yield and the product purity of Li are affected by the need of introducing other reagents in the step of removing the residues.
Although the invention has been described with reference to the preferred embodiments, it should be understood that the invention is not limited thereto, but rather may be modified and varied by those skilled in the art without departing from the spirit and scope of the invention.

Claims (10)

1. A method for directly extracting lithium from lithium-containing brine with low calcium and magnesium content, which is characterized by comprising the following steps:
s1: adding a calcium magnesium ion masking agent to the low calcium magnesium containing lithium brine to stabilize the calcium magnesium in the brine without forming a precipitate in a high pH environment;
s2: mixing low-calcium-magnesium lithium-containing brine added with a calcium-magnesium ion masking agent with an extraction system, and adjusting the pH to be more than 9 to extract lithium in an alkaline environment;
s3: mixing the extraction system loaded with lithium with a stripping agent, and adjusting the pH value to be less than 8 to carry out stripping of lithium;
wherein, in the lithium-containing brine with low calcium and magnesium, pH is 7< 9, ca is 0g/L <1g/L, and Mg is 0g/L <1g/L;
wherein the calcium-magnesium ion masking agent is a chelating agent;
wherein, the high pH environment refers to an environment with pH > 7.
2. The method for directly extracting lithium from lithium-containing brine with low calcium and magnesium according to claim 1, wherein the calcium and magnesium ion masking agent comprises any one or any combination of two or more of ethylenediamine tetraacetic acid, 1, 2-bis (aminomethyl) benzodiphenol, cyclohexylimine tetraacetic acid, ethylenediamine tetraacetic acid N-hydroxyethyl trimethylamine, potassium sodium tartrate, and trisodium nitrilotriacetate.
3. The method for directly extracting lithium from lithium-containing brine of low calcium and magnesium according to claim 1 or 2, wherein in the lithium-containing brine of low calcium and magnesium, li is not less than 0.2g/L, and anions include Cl - 、SO 4 2- And CO 3 2- Any one or any combination of two or more of them.
4. The method of direct extraction of lithium from low calcium magnesium containing lithium brine according to claim 1 or 2, wherein the extraction system is a complex extraction system comprising a chelating extractant, a neutral extractant and a diluent;
wherein the neutral extractant is neutral phosphine comprising any one or a combination of at least two of tributyl phosphate, dimethylheptyl methylphosphonate, trioctylphosphine oxide, trioctyl/hexylphosphine oxide and N, N di- (1-methylheptyl) acetamide;
wherein the chelating extractant comprises any one or a combination of at least two of 2-hydroxy-5-nonylacetophenone oxime, dodecylphenyl-methyl-beta-diketone and 2-hydroxy-5-nonylbenzaldoxime.
5. The method for direct extraction of lithium from low calcium magnesium containing lithium brine according to claim 4 wherein the volume ratio of said neutral extractant to said chelating extractant is (0.2-2): 1.
6. The method for directly extracting lithium from lithium-containing brine with low calcium and magnesium according to claim 1, wherein in step S2, the pH is raised by using a pH adjuster, wherein the pH adjuster is an inorganic salt of sodium or an inorganic salt of potassium.
7. The method for directly extracting lithium from low-calcium magnesium-containing lithium brine according to claim 1, wherein the calcium magnesium ion masking agent accounts for 0.01% -0.1% of the volume of the low-calcium magnesium-containing lithium brine.
8. The method for direct extraction of lithium from low calcium magnesium containing lithium brine according to claim 1, wherein in step S3, the stripping agent comprises any one or more of mineral acid and acid gas.
9. The method according to claim 1, wherein the ratio of the volume of the organic phase to the volume of the aqueous phase is 20:1-1:2 during the back extraction in step S3.
10. The method for direct extraction of lithium from lithium-containing brine of low calcium and magnesium according to claim 1, wherein in step S2, the ratio of the volume of the organic phase to the volume of the aqueous phase is 2:1-1:10.
CN202311257813.4A 2023-09-27 2023-09-27 Method for directly extracting lithium from lithium-containing brine with low calcium and magnesium content Pending CN117248123A (en)

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CN202311257813.4A CN117248123A (en) 2023-09-27 2023-09-27 Method for directly extracting lithium from lithium-containing brine with low calcium and magnesium content

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