CN114394609B - Method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake - Google Patents
Method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake Download PDFInfo
- Publication number
- CN114394609B CN114394609B CN202210073174.5A CN202210073174A CN114394609B CN 114394609 B CN114394609 B CN 114394609B CN 202210073174 A CN202210073174 A CN 202210073174A CN 114394609 B CN114394609 B CN 114394609B
- Authority
- CN
- China
- Prior art keywords
- liquid
- lithium
- hydroxide
- treatment liquid
- filtering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 158
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 144
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000000605 extraction Methods 0.000 claims abstract description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000001914 filtration Methods 0.000 claims abstract description 37
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 31
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 31
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 31
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229910001863 barium hydroxide Inorganic materials 0.000 claims abstract description 25
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000008247 solid mixture Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 27
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 27
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 19
- 229910001424 calcium ion Inorganic materials 0.000 claims description 19
- 238000004364 calculation method Methods 0.000 claims description 15
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 description 20
- 238000000926 separation method Methods 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- -1 hydroxyl ions Chemical class 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application relates to the field of lithium extraction, and particularly discloses a method for preparing lithium hydroxide from a lithium tail liquid extracted from a salt lake. A method for preparing lithium hydroxide from lithium tail liquid extracted from a salt lake comprises the following steps: 1) Adding calcium hydroxide into the lithium extraction tail liquid, heating, stirring, filtering, and collecting the liquid to obtain a first treatment liquid; 2) Adding oxalic acid into the first treatment liquid, heating, stirring, filtering, and taking liquid to obtain a second treatment liquid; 3) Adding barium hydroxide into the second treatment liquid, heating, stirring, filtering, and taking liquid to obtain a third treatment liquid; 4) Adding sodium hydroxide into the third treatment liquid, heating, stirring, filtering, and collecting the liquid to obtain a fourth treatment liquid; 5) Evaporating and drying the fourth treatment liquid to obtain a solid mixture; 6) Heating the solid mixture to 650-700 ℃, filtering, taking liquid, cooling to 400-450 ℃, filtering, and taking solid to obtain lithium chloride; 7) And (3) electrolyzing the lithium chloride to obtain lithium hydroxide. The application has the effect of fully utilizing the lithium extraction tail liquid.
Description
Technical Field
The application relates to the field of lithium extraction, in particular to a method for preparing lithium hydroxide from a lithium tail liquid extracted from a salt lake.
Background
With the development of technology, lithium is an important resource, no simple substance lithium exists in nature, the lithium needs to be extracted from ore or salt water, and the extraction of lithium from salt lakes is one of important means for extracting lithium.
The lithium extraction in the salt lake is mainly carried out by extracting lithium carbonate from salt water containing lithium through an evaporation method, but because the lithium carbonate is a precipitate, certain solubility still exists in water, so that certain lithium ions are still contained in the lithium extraction tail liquid, and in the process of extracting lithium from the salt lake, a large amount of magnesium ions are left, so that the content of magnesium ions in the lithium extraction tail liquid is higher, water is completely evaporated through an evaporation method, purer lithium salt cannot be obtained, a large amount of magnesium salts are contained in an obtained product, the lithium extraction tail liquid is difficult to utilize, the lithium ions in the lithium extraction tail liquid are difficult to recover, and resource waste is caused, so that the improvement space is provided.
Disclosure of Invention
In order to fully utilize the lithium extraction tail liquid, the application provides a method for preparing lithium hydroxide by using the lithium extraction tail liquid of a salt lake.
The application provides a method for preparing lithium hydroxide by using a lithium tail liquid extracted from a salt lake, which adopts the following technical scheme:
a method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake comprises the following steps:
step 1), adding lithium extraction tail liquid into a container, adding calcium hydroxide into the lithium extraction tail liquid, heating, stirring, filtering, and taking liquid to obtain a first treatment liquid;
step 2), oxalic acid is added into the first treatment liquid, heating and stirring are carried out, and liquid is filtered, so that a second treatment liquid is obtained;
step 3), adding barium hydroxide into the second treatment liquid, heating, stirring, filtering, and taking liquid to obtain a third treatment liquid;
step 4), adding sodium hydroxide into the third treatment liquid, heating, stirring, filtering, and taking liquid to obtain a fourth treatment liquid;
step 5), evaporating and drying the fourth treatment liquid to obtain a solid mixture;
step 6), heating the solid mixture to 650-700 ℃, filtering at the constant temperature of 650-700 ℃, taking liquid, cooling to 400-450 ℃, filtering at the constant temperature of 400-450 ℃, and taking solid to obtain lithium chloride;
and 7) electrolyzing the lithium chloride to prepare the lithium hydroxide.
By adopting the technical scheme, the magnesium hydroxide precipitate is generated by adding calcium hydroxide and heating and reacting, and can be removed by filtering, so that the magnesium ion concentration is greatly reduced; adding oxalic acid, heating, reacting to generate calcium oxalate precipitate, and filtering to remove calcium oxalate precipitate, so that calcium ions introduced during calcium hydroxide input and calcium ions in lithium extraction tail liquid are removed, and the concentration of calcium ions is greatly reduced; adding barium hydroxide, heating, reacting to generate barium sulfate precipitate, and filtering to remove the barium sulfate precipitate, thereby reducing the concentration of sulfate ions in the lithium extraction tail liquid; the PH value of the system is regulated by adding sodium hydroxide, and magnesium ions possibly remained are reacted into magnesium hydroxide, and the concentration of the magnesium ions in the lithium extraction tail liquid is further reduced by filtering; the water is evaporated through evaporation and drying, so that a solid mixture is obtained, the fourth treatment liquid mainly contains lithium ions, potassium ions, sodium ions, hydroxyl ions and chloride ions due to the addition of sodium hydroxide, after evaporation and drying, the solid mixture mainly comprises lithium chloride, sodium hydroxide, potassium hydroxide, sodium chloride and potassium chloride, the lithium chloride, the sodium hydroxide and the potassium hydroxide are melted through heating, the sodium chloride and the potassium chloride are still kept in a solid state due to higher melting points, the sodium chloride and the potassium chloride can be removed through filtering, and then cooled to 400-450 ℃, at the moment, the lithium chloride is in a solid state due to higher melting points, the sodium hydroxide and the potassium hydroxide have low melting points and are in a liquid state, pure lithium chloride can be separated through filtering, lithium hydroxide can be obtained through electrolysis, so that lithium hydroxide tail liquid can be fully utilized, lithium ions are recovered from the lithium hydroxide tail liquid, resource waste is reduced, and the lithium chloride is pure so that the purity of lithium hydroxide generated through electrolysis is higher, so that the utilization effect of the lithium hydroxide tail liquid is better.
Preferably, in the step 1), the lithium extraction tail solution is heated to 98-100 ℃.
By adopting the technical scheme, the specific heating temperature is selected, so that the magnesium hydroxide is more sufficient in reaction, the content of magnesium ions is better reduced, and finally the obtained lithium hydroxide is purer.
Preferably, in the step 2), the first treatment liquid is heated to 85-88 ℃.
By adopting the technical scheme, the specific heating temperature is selected, so that the calcium oxalate reaction is more sufficient, the content of calcium ions is better reduced, and the finally obtained lithium hydroxide is purer.
Preferably, in the step 3), the second treatment liquid is heated to 60-62 ℃.
By adopting the technical scheme, the barium sulfate reaction is more sufficient by selecting the specific heating temperature, the content of sulfate ions is better reduced, and finally the obtained lithium hydroxide is purer.
Preferably, in the step 4), the third treating liquid is heated to 98-100 ℃.
By adopting the technical scheme, unreacted magnesium ions are better reacted to generate magnesium hydroxide by selecting a specific heating temperature, and the content of magnesium ions is better reduced after filtration, so that the finally obtained lithium hydroxide is purer.
Preferably, in the step 4), the third treatment solution is cooled to 5-10 ℃ and then filtered.
By adopting the technical scheme, the solubility of magnesium hydroxide is further reduced by cooling, and the effect of removing magnesium ions is better.
Preferably, in the step 1), the content of each element in the lithium extraction tail liquid is measured, and the input amount of calcium hydroxide, oxalic acid and barium hydroxide is calculated according to the content of each element.
By adopting the technical scheme, the removal effect of magnesium ions, calcium ions and sulfate ions is better through calculation, and the condition of introducing new impurities is reduced, so that the obtained lithium hydroxide is purer.
Preferably, the calculation formula of the input amount (mol) of the input amounts of calcium hydroxide, oxalic acid and barium hydroxide is as follows:
calcium hydroxide (mol) =magnesium ion (mol) ×1.1 in lithium extraction tail solution;
oxalic acid (mol) =calcium ions (mol) ×1.1+ in lithium extraction tail liquid;
barium hydroxide (mol) =sulfate ion (mol) ×0.98 in lithium extraction tail solution.
By adopting the technical scheme, magnesium ions are better removed through excessive calcium hydroxide, calcium ions are better removed through excessive oxalic acid, the introduction of barium ions is reduced through a small amount of barium hydroxide, the content of sulfate ions is low, trace sulfate ions remain, and the influence on the quality of lithium hydroxide is small.
Preferably, in the step 4), sodium hydroxide is added to adjust the pH value of the third treatment solution to be more than or equal to 8.
By adopting the technical scheme, the third treatment liquid is alkaline, so that the effect of removing magnesium ions is better, and the quality of the obtained lithium hydroxide is higher.
In summary, the application has the following beneficial effects:
1. according to the application, calcium hydroxide is added and heated, so that the concentration of magnesium ions is greatly reduced; oxalic acid is added and heated, so that the concentration of calcium ions is greatly reduced; the concentration of sulfate ions in the lithium extraction tail liquid is reduced by adding barium hydroxide and heating; the PH value of the system is regulated by adding sodium hydroxide, so that the concentration of magnesium ions in the lithium extraction tail liquid is further reduced; through evaporation drying for the moisture evaporates, obtains the solid mixture, through heating, gets rid of sodium chloride, potassium chloride, then cools off to 400-450 ℃, through filtering, separates pure lithium chloride, through the electrolysis, can obtain lithium hydroxide for the lithium ion is retrieved to salt lake lithium extraction tail liquid from extracting tail liquid, reduces the wasting of resources, and because lithium chloride is comparatively pure, makes the lithium hydroxide of electrolysis lithium with the purity of formation higher, makes the salt lake extract lithium tail liquid's result of utilization better.
2. In the application, magnesium ions are preferably removed better through excessive calcium hydroxide, calcium ions are removed better through excessive oxalic acid, the introduction of barium ions is reduced through a small amount of barium hydroxide, the sulfate ion content is low, trace sulfate ions remain, and the influence on the quality of lithium hydroxide is less.
3. In the present application, it is preferable that the third treatment liquid is made alkaline so that the effect of removing magnesium ions is better and the quality of lithium hydroxide obtained is higher.
Detailed Description
The present application will be described in further detail with reference to examples.
The main ion content of the lithium extraction tail solution used in the following examples is shown in Table 1.
TABLE 1
| Major ions | Concentration by mass (g/L) |
| Lithium ion | 1.25 |
| Magnesium ions | 56.15 |
| Calcium ion | 0.039 |
| Potassium ion | 0.38 |
| Sodium ions | 0.22 |
| Chloride ions | 126.17 |
| Boron ions | 0.13 |
| Sulfate ion | 5.32 |
| Iron ions | 0.00073 |
Example 1
A method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake comprises the following steps:
step 1), 1L of lithium extraction tail liquid is put into a container, the content of main ions in the lithium extraction tail liquid is sampled and analyzed, and the content of the main ions in the lithium extraction tail liquid can be analyzed by an ion analyzer, an atomic absorption spectrometer and the like, and the details of the content of the main ions in the lithium extraction tail liquid in the embodiment are shown in table 1.
And calculating the calcium hydroxide input amount according to the magnesium ion concentration in table 1, then adding calcium hydroxide into the lithium extraction tail liquid, heating to 98 ℃, stirring for 5min at the rotating speed of 30r/min, filtering by a screen, carrying out solid-liquid separation, and taking liquid to obtain the first treatment liquid.
The calculation formula of the calcium hydroxide input is as follows:
calcium hydroxide (mol) =magnesium ion (mol) ×1.1 in lithium extraction tail.
The amount of the substance is calculated in the calculation, and the amount of the substance of calcium hydroxide is calculated from the amount of the substance converted into magnesium ions by the magnesium ion concentration, and then converted into the mass of calcium hydroxide.
Step 2), according to the calcium ion concentration in table 1 and the calcium hydroxide input amount in step 1), oxalic acid is added into the first treatment liquid, the oxalic acid is heated to 85 ℃, the rotating speed is 30r/min, stirring is carried out for 5min, filtering is carried out through a screen, solid-liquid separation is carried out, and liquid is taken out, thus obtaining the second treatment liquid.
The calculation formula of the oxalic acid input is as follows:
oxalic acid (mol) =calcium ion (mol) ×1.1+ of calcium hydroxide (mol) added in lithium extraction tail liquid.
The amount of the substance is calculated in the calculation, and the amount of the substance of oxalic acid is calculated from the amount of the substance converted into calcium ions by the calcium ion concentration, and then converted into the mass of oxalic acid.
And 3) calculating the input amount of barium hydroxide according to the sulfate ion concentration in the table 1, then adding barium hydroxide into the second treatment liquid, heating to 60 ℃, stirring for 5min at the rotating speed of 30r/min, filtering by a screen, carrying out solid-liquid separation, and taking liquid to obtain a third treatment liquid.
The calculation formula of the input amount of barium hydroxide is as follows:
barium hydroxide (mol) =sulfate ion (mol) ×0.98 in lithium extraction tail solution.
The amount of the substance is calculated in the calculation, and the amount of the substance of barium hydroxide is calculated from the amount of the substance converted into sulfate ions by the sulfate ion concentration, and then converted into the mass of barium hydroxide.
And 4) adding sodium hydroxide into the third treatment liquid until the PH value of the third treatment liquid is 10, heating to 98 ℃, stirring for 5min at the rotating speed of 30r/min, filtering by a screen, carrying out solid-liquid separation, and taking liquid to obtain fourth treatment liquid.
And 5) throwing the fourth treatment liquid into a rotary evaporator, and evaporating and drying to obtain a solid mixture.
And 6) putting the solid mixture into a crucible, heating to 650 ℃, filtering through a screen at the constant temperature of 650 ℃, carrying out solid-liquid separation, taking liquid, cooling the liquid to 400 ℃, filtering through the screen at the constant temperature of 400 ℃, carrying out solid-liquid separation, and taking solid to obtain the lithium chloride.
Step 7), preparing lithium hydroxide by an ionic membrane electrolysis method, dissolving lithium chloride in deionized water to prepare an anode solution with the mass fraction of 22%, dissolving lithium hydroxide in the deionized water to prepare a cathode solution with the mass fraction of 2%, and the current density of 1.2A/m 2 And (3) evaporating the prepared lithium hydroxide solution through a rotary evaporator at the temperature of 25 ℃ by using a Nafion membrane as an ion membrane to obtain a solid, and drying to obtain the lithium hydroxide.
Example 2
A method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake comprises the following steps:
step 1), 1L of lithium extraction tail liquid is put into a container, the content of main ions in the lithium extraction tail liquid is sampled and analyzed, and the content of the main ions in the lithium extraction tail liquid can be analyzed by an ion analyzer, an atomic absorption spectrometer and the like, and the details of the content of the main ions in the lithium extraction tail liquid in the embodiment are shown in table 1.
And calculating the calcium hydroxide input amount according to the magnesium ion concentration in table 1, then adding calcium hydroxide into the lithium extraction tail liquid, heating to 100 ℃, stirring for 5min at the rotating speed of 30r/min, filtering by a screen, carrying out solid-liquid separation, and taking liquid to obtain a first treatment liquid.
The calculation formula of the calcium hydroxide input is as follows:
calcium hydroxide (mol) =magnesium ion (mol) ×1.1 in lithium extraction tail.
The amount of the substance is calculated in the calculation, and the amount of the substance of calcium hydroxide is calculated from the amount of the substance converted into magnesium ions by the magnesium ion concentration, and then converted into the mass of calcium hydroxide.
Step 2), according to the calcium ion concentration in table 1 and the calcium hydroxide input amount in step 1), oxalic acid is added into the first treatment liquid, the oxalic acid is heated to 88 ℃, the rotating speed is 30r/min, stirring is carried out for 5min, filtering is carried out through a screen, solid-liquid separation is carried out, and liquid is taken out, thus obtaining the second treatment liquid.
The calculation formula of the oxalic acid input is as follows:
oxalic acid (mol) =calcium ion (mol) ×1.1+ of calcium hydroxide (mol) added in lithium extraction tail liquid.
The amount of the substance is calculated in the calculation, and the amount of the substance of oxalic acid is calculated from the amount of the substance converted into calcium ions by the calcium ion concentration, and then converted into the mass of oxalic acid.
And 3) calculating the input amount of barium hydroxide according to the sulfate ion concentration in the table 1, then adding barium hydroxide into the second treatment liquid, heating to 62 ℃, stirring for 5min at the rotating speed of 30r/min, filtering by a screen, carrying out solid-liquid separation, and taking liquid to obtain a third treatment liquid.
The calculation formula of the input amount of barium hydroxide is as follows:
barium hydroxide (mol) =sulfate ion (mol) ×0.98 in lithium extraction tail solution.
The amount of the substance is calculated in the calculation, and the amount of the substance of barium hydroxide is calculated from the amount of the substance converted into sulfate ions by the sulfate ion concentration, and then converted into the mass of barium hydroxide.
And 4) adding sodium hydroxide into the third treatment liquid until the PH value of the third treatment liquid is 10, heating to 100 ℃, stirring for 5min at the rotating speed of 30r/min, cooling to 5 ℃, filtering by a screen, and carrying out solid-liquid separation to obtain a liquid to obtain a fourth treatment liquid.
And 5) throwing the fourth treatment liquid into a rotary evaporator, and evaporating and drying to obtain a solid mixture.
And 6) putting the solid mixture into a crucible, heating to 700 ℃, filtering through a screen at the constant temperature of 700 ℃, carrying out solid-liquid separation, taking liquid, cooling the liquid to 450 ℃, filtering through the screen at the constant temperature of 450 ℃, carrying out solid-liquid separation, and taking solid to obtain the lithium chloride.
Step 7), preparing lithium hydroxide by an ionic membrane electrolysis method, dissolving lithium chloride in deionized water to prepare an anode solution with the mass fraction of 22%, dissolving lithium hydroxide in the deionized water to prepare a cathode solution with the mass fraction of 2%, and the current density of 1.2A/m 2 And (3) evaporating the prepared lithium hydroxide solution through a rotary evaporator at the temperature of 25 ℃ by using a Nafion membrane as an ion membrane to obtain a solid, and drying to obtain the lithium hydroxide.
Example 3
The method for preparing lithium hydroxide by extracting lithium tail liquid from salt lake is different from example 2 only in that:
and 4) adding sodium hydroxide into the third treatment liquid until the PH value of the third treatment liquid is 10, heating to 100 ℃, stirring for 5min at the rotating speed of 30r/min, cooling to 10 ℃, filtering by a screen, and carrying out solid-liquid separation to obtain a liquid to obtain a fourth treatment liquid.
Experiment 1
The mass fractions of the main components in the lithium hydroxide monohydrate of each example were detected according to GB/T11064 method for chemical analysis of lithium carbonate, lithium hydroxide monohydrate, lithium chloride and compared with the standards in GB/T26008-2010 Battery grade lithium hydroxide monohydrate.
The detection results are shown in Table 2.
TABLE 2
According to the data in Table 2, the lithium hydroxide prepared by the method in examples 1-3 meets the standard of battery grade lithium hydroxide monohydrate, has higher purity, realizes the recycling of lithium extraction tail liquid, has better effect, and the prepared by-product can be used in industry to generate higher economic value.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (9)
1. A method for preparing lithium hydroxide by extracting lithium tail liquid from a salt lake is characterized by comprising the following steps of: the method comprises the following steps:
step 1), adding lithium extraction tail liquid into a container, adding calcium hydroxide into the lithium extraction tail liquid, heating, stirring, filtering, and taking liquid to obtain a first treatment liquid;
step 2), oxalic acid is added into the first treatment liquid, heating and stirring are carried out, and liquid is filtered, so that a second treatment liquid is obtained;
step 3), adding barium hydroxide into the second treatment liquid, heating, stirring, filtering, and taking liquid to obtain a third treatment liquid;
step 4), adding sodium hydroxide into the third treatment liquid, heating, stirring, filtering, and taking liquid to obtain a fourth treatment liquid;
step 5), evaporating and drying the fourth treatment liquid to obtain a solid mixture;
step 6), heating the solid mixture to 650-700 ℃, filtering at the constant temperature of 650-700 ℃, taking liquid, cooling to 400-450 ℃, filtering at the constant temperature of 400-450 ℃, and taking solid to obtain lithium chloride;
and 7) electrolyzing the lithium chloride to prepare the lithium hydroxide.
2. The method for preparing lithium hydroxide by using the lithium extraction tail liquid of salt lake according to claim 1, which is characterized in that: in the step 1), the lithium extraction tail liquid is heated to 98-100 ℃.
3. The method for preparing lithium hydroxide by using the lithium extraction tail liquid of salt lake according to claim 1, which is characterized in that: in the step 2), the first treatment liquid is heated to 85-88 ℃.
4. The method for preparing lithium hydroxide by using the lithium extraction tail liquid of salt lake according to claim 1, which is characterized in that: in the step 3), the second treatment liquid is heated to 60-62 ℃.
5. The method for preparing lithium hydroxide by using the lithium extraction tail liquid of salt lake according to claim 1, which is characterized in that: in the step 4), the third treatment liquid is heated to 98-100 ℃.
6. The method for preparing lithium hydroxide from the lithium extraction tail liquid of the salt lake according to claim 5, which is characterized in that: in the step 4), the third treatment liquid is cooled to 5-10 ℃ and then filtered.
7. The method for preparing lithium hydroxide by using the lithium extraction tail liquid of salt lake according to claim 1, which is characterized in that: in the step 1), the content of each element in the lithium extraction tail liquid is measured, and the input amount of calcium hydroxide, oxalic acid and barium hydroxide is calculated according to the content of each element.
8. The method for preparing lithium hydroxide from the lithium extraction tail liquid of the salt lake according to claim 7, which is characterized in that: the calculation formula of the input amount of the calcium hydroxide, the oxalic acid and the barium hydroxide is as follows:
calcium hydroxide = magnesium ions x 1.1 in the lithium extraction tail solution;
oxalic acid = calcium ions in lithium extraction tail liquid x 1.1+ input calcium hydroxide;
barium hydroxide = sulfate ions x 0.98 in lithium extraction tail solution;
the input is in mol.
9. The method for preparing lithium hydroxide from the lithium extraction tail liquid of the salt lake according to claim 8, which is characterized in that: in the step 4), sodium hydroxide is added to adjust the pH value of the third treatment liquid to be more than or equal to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210073174.5A CN114394609B (en) | 2022-01-21 | 2022-01-21 | Method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210073174.5A CN114394609B (en) | 2022-01-21 | 2022-01-21 | Method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114394609A CN114394609A (en) | 2022-04-26 |
| CN114394609B true CN114394609B (en) | 2023-11-24 |
Family
ID=81231921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210073174.5A Active CN114394609B (en) | 2022-01-21 | 2022-01-21 | Method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114394609B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010105508A1 (en) * | 2009-03-18 | 2010-09-23 | 中南大学 | Method for extracting lithium salt from low-magnesium/lithium ratio brine of saline with calcium circulation solid-phase conversion process |
| CN109824066A (en) * | 2019-04-18 | 2019-05-31 | 王东升 | A method of LITHIUM BATTERY lithium hydroxide is prepared by industrial level lithium carbonate |
| WO2021190402A1 (en) * | 2020-03-25 | 2021-09-30 | 意定(上海)信息科技有限公司 | Method for preparing lithium hydroxide from lithium-containing low-magnesium brine |
-
2022
- 2022-01-21 CN CN202210073174.5A patent/CN114394609B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010105508A1 (en) * | 2009-03-18 | 2010-09-23 | 中南大学 | Method for extracting lithium salt from low-magnesium/lithium ratio brine of saline with calcium circulation solid-phase conversion process |
| CN109824066A (en) * | 2019-04-18 | 2019-05-31 | 王东升 | A method of LITHIUM BATTERY lithium hydroxide is prepared by industrial level lithium carbonate |
| WO2021190402A1 (en) * | 2020-03-25 | 2021-09-30 | 意定(上海)信息科技有限公司 | Method for preparing lithium hydroxide from lithium-containing low-magnesium brine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114394609A (en) | 2022-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Song et al. | Recovery of lithium from spent lithium-ion batteries using precipitation and electrodialysis techniques | |
| US20220372592A1 (en) | Method for extracting lithium by means of extraction-back extraction separation and purification | |
| KR102545219B1 (en) | Method for treating lithium-containing materials containing HCl sparge | |
| KR102341052B1 (en) | Methods for treating lithium-containing materials | |
| US10597305B2 (en) | Methods for treating lithium-containing materials | |
| CN106542512A (en) | Using the high-purity phosphoric acid lithium preparation method of the lithium waste liquid of old and useless battery | |
| CN104745823B (en) | Method for recycling lithium from waste lithium ion battery | |
| CA2762601A1 (en) | Lithium carbonate production from brine | |
| JP2001525313A (en) | Purification method of lithium carbonate | |
| US20210344058A1 (en) | Process for recovering lithium and transition metals from waste cathode of spent lithium ion battery | |
| CN110550643A (en) | process for recovering and preparing battery-grade lithium salt from sodium-separating mother liquor | |
| Grágeda et al. | Purification of brines by chemical precipitation and ion‐exchange processes for obtaining battery‐grade lithium compounds | |
| WO2018087697A1 (en) | Methods and systems for preparing lithium hydroxide | |
| CN113501536A (en) | Method for preparing aluminum fluoride product by multi-waste combined treatment and aluminum fluoride product | |
| KR20120089515A (en) | Method for extracting economically lithium phosphate with high purity from brine | |
| CN114394609B (en) | Method for preparing lithium hydroxide from lithium tail liquid extracted from salt lake | |
| CN102372295A (en) | Method for separating magnesium and concentrating lithium in brine | |
| US3357800A (en) | Purification of magnesium chloride with alcohol | |
| TW202322450A (en) | Process | |
| CN112408436B (en) | Method for separating sodium and lithium by partially ionizing sodium-lithium-containing brine | |
| CN112239221B (en) | Method for extracting rubidium chloride from rubidium-containing high-salinity brine | |
| CN112456518B (en) | Method for separating and concentrating sodium and lithium from sodium-lithium-containing brine | |
| CN113651344A (en) | Method for purifying magnesium chloride by using salt lake brine | |
| US3306712A (en) | Extraction of lithium halides from calcium-containing brines in the presence of urea and alcohol-ketone | |
| CN111635999A (en) | Method for extracting lithium from lithium-containing brine and preparing lithium hydroxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230412 Address after: Room 101, Building 6, No. 5 Weifeng Road, Dongguan City, Guangdong Province, 523128 Applicant after: Guangdong Songquan Environmental Protection Equipment Co.,Ltd. Address before: 523888 building 6, No. 5, Weifeng Road, Dongcheng Street, Dongguan City, Guangdong Province Applicant before: GUANGDONG TAIQUAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231013 Address after: 523888 building 6, No. 5, Weifeng Road, Dongcheng Street, Dongguan City, Guangdong Province Applicant after: GUANGDONG TAIQUAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: Room 101, Building 6, No. 5 Weifeng Road, Dongguan City, Guangdong Province, 523128 Applicant before: Guangdong Songquan Environmental Protection Equipment Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 523888 building 6, No. 5, Weifeng Road, Dongcheng Street, Dongguan City, Guangdong Province Patentee after: Guangdong Taiquan Technology Co.,Ltd. Country or region after: China Address before: 523888 building 6, No. 5, Weifeng Road, Dongcheng Street, Dongguan City, Guangdong Province Patentee before: GUANGDONG TAIQUAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Country or region before: China |