CN113149041B - Method for concentrating and recycling lithium precipitation mother liquor lithium in lithium carbonate production - Google Patents
Method for concentrating and recycling lithium precipitation mother liquor lithium in lithium carbonate production Download PDFInfo
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- CN113149041B CN113149041B CN202110172876.4A CN202110172876A CN113149041B CN 113149041 B CN113149041 B CN 113149041B CN 202110172876 A CN202110172876 A CN 202110172876A CN 113149041 B CN113149041 B CN 113149041B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 99
- 239000012452 mother liquor Substances 0.000 title claims abstract description 37
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 28
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- 238000001556 precipitation Methods 0.000 title claims description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 47
- 239000002985 plastic film Substances 0.000 claims abstract description 27
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- 238000000748 compression moulding Methods 0.000 claims abstract description 5
- 230000004913 activation Effects 0.000 claims abstract description 3
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 31
- 238000000605 extraction Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 239000010413 mother solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims description 3
- 150000002642 lithium compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052806 inorganic carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 4
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 150000003608 titanium Chemical class 0.000 abstract 1
- 238000007873 sieving Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- -1 rechargeable battery Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 206010026749 Mania Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005467 ceramic manufacturing process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005370 electroosmosis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000000147 hypnotic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940125725 tranquilizer Drugs 0.000 description 1
- 239000003204 tranquilizing agent Substances 0.000 description 1
- 230000002936 tranquilizing effect Effects 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
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for concentrating and recycling lithium-precipitated mother liquor in lithium carbonate production, which comprises the steps of carrying out sanding treatment on titanium-based lithium, then carrying out spray drying to obtain titanium-based lithium powder, mixing the titanium-based lithium powder with PE resin powder, a dispersing aid, a pore-forming agent and a cross-linking agent, carrying out compression molding after uniform mixing to obtain a titanium-based lithium-based plastic sheet with proper thickness, carrying out activation treatment on the titanium-based lithium-based plastic sheet to obtain a titanium-based lithium ion sieve, immersing the activated titanium-based lithium ion sieve in the lithium-precipitated mother liquor, extracting lithium ions from the lithium-precipitated mother liquor, and desorbing lithium ions from the ion sieve through an acid solution to obtain a lithium-rich solution with high lithium content and a regenerated titanium-based lithium ion sieve. The ion sieve can be repeatedly recycled, has no dissolution loss and pulverization, has long service life and high selectivity, and the lithium content of the concentrated lithium-rich solution can reach about 12000ppm and the lithium recovery rate can reach more than 90 percent by controlling the solid-to-liquid ratio.
Description
Technical Field
The invention relates to a method for concentrating and recycling lithium deposition mother liquor in lithium carbonate production, in particular to a method for concentrating and recycling lithium ions in lithium deposition mother liquor by utilizing a titanium-based lithium ion sieve with high selectivity and high capacity.
Background
The lithium carbonate can be used as a basic lithium salt of lithium, and can be directly used as a raw material for preparing various lithium salts and compounds thereof with high added value. In the production of glass, especially cathode-ray tube, heat-resistant glass, glass fiber and optical glass, lithium carbonate can lower the melting temperature of glass, raise the density and strength of glass and improve the viscosity, thermal expansion and other important properties of glass. In the ceramic manufacturing process, the proper amount of lithium carbonate is added to increase the transparency of the product, the wear resistance, the expansion coefficient and the melting temperature, the fuel consumption and the service life of the melting furnace.
In medicine, lithium carbonate is useful as a hypnotic and tranquilizer and has become the drug of choice for the treatment of mania. In the aspect of aluminum smelting industry, the carbon material containing lithium carbonate is used for replacing the common active carbon material to be used as the anode, so that the overpotential of the anode can be reduced, and 300-600 kW.h of electricity can be saved in the production of each ton of aluminum. In the field of batteries, lithium carbonate is an important raw material for producing electrode materials such as lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganate, lithium nickel cobalt oxide and the like, and mixtures thereof. Lithium carbonate also has wide application in lubricant, rechargeable battery, air conditioner and other industries.
The conventional lithium carbonate production process is to remove impurities from an enriched lithium salt solution, slightly dissolve lithium carbonate in water, and the solubility of lithium carbonate is reduced along with the temperature rise, add excessive sodium carbonate into the lithium salt solution to form lithium carbonate precipitate, then heat the solution to above 90 ℃ to improve the yield, and obtain solid lithium carbonate after solid-liquid separation. Because a large amount of sodium carbonate is used in the production process, part of sodium ions are inevitably carried away when lithium carbonate precipitates are formed, so that the solid lithium carbonate obtained after solid-liquid separation is also required to be subjected to a plurality of high-temperature centrifugal water washing procedures to remove the sodium ions. The liquid obtained by solid-liquid separation and the washing liquid obtained by water washing contain a large amount of lithium ions and sodium ions, and the concentration of the sodium ions is generally tens times of that of the lithium ions.
This portion of the lithium precipitation mother liquor and the washing liquor, if discharged directly, results in a significant loss of lithium. If the conventional high-temperature concentration and recovery method is adopted, not only is the energy consumption high and the production cost high, but also a large amount of sodium salt is saturated and separated out while the lithium carbonate is separated out. Because of the strong alkalinity and high temperature characteristics of the lithium precipitation mother liquor, the electroosmosis membrane and the aluminum lithium ion sieve adopted by conventional lithium extraction cannot be used in the environment. And when the manganese lithium ion sieve is used for removing lithium, the phenomenon of dissolution loss exists, so that the service life is shortened.
Disclosure of Invention
The invention aims to provide a plastic sheet type titanium lithium ion sieve with high lithium ion adsorption capacity, high selectivity and long service life, which is used for concentrating and recovering lithium in lithium precipitation mother liquor.
The method of the invention comprises the following steps:
preparing a titanium lithium ion sieve:
a. mixing titanium lithium compound with deionized water, and stirring to prepare slurry;
b. performing sanding treatment on the slurry by using zirconium beads, and performing spray drying on the sanded slurry to obtain titanium lithium compound powder;
c. mixing titanium lithium compound powder with PE resin powder, a dispersing auxiliary agent, a pore-forming agent and a cross-linking agent according to a certain proportion, and preparing a titanium lithium compound plastic sheet with the thickness of 0.5-1.5 mm by a compression molding machine after uniformly mixing;
d. immersing a plastic sheet in deionized water, slowly adding an acid solution into the deionized water, dropwise adding the solution to control the pH value to be between 1.0 and 2.0, and taking out the titanium lithium compound plastic sheet after the pH value is stable and unchanged to obtain an activated titanium lithium ion sieve;
e. pumping the lithium precipitation mother liquor into an ion exchange tank, and cooling to 55-75 ℃;
f. immersing the activated titanium-series lithium ion sieve obtained in the step (d) in a lithium precipitation mother solution, observing the PH value of the lithium precipitation mother solution, and taking out the titanium-series lithium ion sieve after the PH value is stable and does not change any more;
g. immersing the titanium lithium ion sieve after lithium extraction in deionized water, slowly adding dilute acid solution into the deionized water, dropwise adding the dilute acid solution, controlling the pH value to be 0.5-1.5, and taking out the titanium lithium ion sieve after the pH value is stable and unchanged, thus obtaining lithium-rich solution with high lithium content and the regenerated titanium lithium ion sieve.
Wherein the titanium-based lithium compound in the step a has a molecular formula of Li 2 TiO 3 The mass fraction of the active ingredients of the structural compound is not less than 99%, and the mass fraction of the screen residue is not more than 0.01%. The titanium lithium compound and deionized water are mixed according to m (lithiate) ：m (deionized water) Mixing was performed =1:2.
In the step b, the titanium lithium compound powder with the required particle size can be obtained by selecting zirconium beads with the particle size of 0.6-0.8 mu m for sanding treatment and then selecting a spray drying spray nozzle with the proper pore diameter, and the particle size D is controlled 50 D is less than or equal to 300nm 50 ≤800nm。
In the step c, the mixing mass ratio of the titanium lithium compound to the PE resin powder, the dispersing auxiliary agent, the pore-forming agent and the cross-linking agent is 6:2.5:0.2:1:0.3, wherein the pore-forming agent is inorganic carbonate, and comprises one or a mixture of sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate, and the pore-forming agent is used for reacting with acid to generate soluble salt in the subsequent activation step, so that the plastic sheet generates a porous structure to increase the lithium extraction efficiency.
In the step c, the thickness of the titanium-based lithium compound plastic sheet which is molded by the molding machine is 0.5mm to 1.5mm, preferably 1.0mm.
In step d, the acid solution isAnd the final pH value of the mixed solution is controlled to be 1.0-2.0, preferably the pH value is 1.5. Plastic sheet in m (Plastic sheet) ：m (deionized water) =1:1 immersed in deionized water at 50-65 ℃.
In the step e, the lithium precipitation mother liquor needs to be cooled to be used at 55-75 ℃, the too high temperature can cause softening of plastic particles, the lithium extraction efficiency and the recycling times of the ion sieve are affected, and the too low temperature can affect the lithium extraction efficiency.
In the step f, the ratio of the ion sieve to the lithium precipitation mother solution is controlled to be 1: 8-1: 12, preferably in a ratio of 1:10.
In step f, the end point of the completion of the lithium exchange is to observe that the pH is stable and no longer changing. The lithium extraction mechanism of the titanium ion sieve is H + And Li (lithium) + Is an exchange process of (1) absorbing Li during lithium extraction + Release H + This results in a decrease in the pH, which no longer decreases as the exchange is completed.
In the step g, the ion sieve is immersed in deionized water according to the mass ratio of 2:1, so that the lithium concentration of the subsequent lithium removal solution can be improved, and the maximum release of lithium ions can be ensured. The desorption speed can be improved by adjusting the reaction temperature to 50-65 ℃.
In step g, the acid solution isAnd the final pH value of the mixed solution is controlled to be 0.5-1.5, preferably the pH value is 1.0.
Compared with the prior art, the invention has the following advantages:
(1) Compared with the conventional lithium extraction process and the inapplicability of materials in lithium precipitation mother liquor, the invention adopts the titanium lithium ion sieve as a means for extracting lithium, can further improve the yield by about 30% on the production scale of the existing factory, and greatly improves the benefit of the factory.
(2) According to the method for concentrating and recycling lithium in lithium carbonate production, through years of intensive research, the inventor improves a compression molding sheet preparation formula, so that on one hand, the plasticity of a plastic sheet is improved, the recycling life is prolonged, no dissolution loss and pulverization are caused in the use process, on the other hand, the lithium extraction efficiency can be greatly improved and improved by adding a pore-forming agent, the lithium content in the original lithium-precipitating mother solution is about 1800ppm, the lithium content of the concentrated lithium-rich solution can reach about 12000ppm by controlling the solid-to-liquid ratio, the method can be directly used for producing lithium carbonate, and the lithium recovery rate in the lithium-precipitating mother solution is up to more than 90%.
(3) The lithium extraction and lithium removal are carried out in a plastic sheet immersed mode, the equipment and process flow is simple, the industrial production cost is low, and the large-area popularization is convenient.
(4) Compared with a manganese ion sieve and an aluminum ion sieve, the titanium lithium ion sieve prepared by the method has higher adsorption capacity, and the lithium ion concentration in the lithium-rich solution after lithium removal is more than 12g/L.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
Example 1
Mixing titanium lithium compound with deionized water according to m (lithiate) ：m (deionized water) Mixing the materials in a ratio of (1:2), and uniformly stirring to prepare slurry; sanding the slurry with 0.6-0.8 mu m zirconium beads, and spray drying to obtain D 50 Titanium-based lithiate powder of =347 nm; mixing titanium lithium compound powder with PE resin powder, a dispersing auxiliary agent, a pore-forming agent and a crosslinking agent according to a mass ratio of 6:2.5:0.2:1:0.3, mixing evenly, and then compacting to prepare a titanium lithium compound plastic sheet with the thickness of 0.5 mm; the plastic sheet is divided into m parts (Plastic sheet) ：m (deionized water) =1:1 immersed in deionized water at 50 ℃, to which deionized water was slowly addedThe pH value of the diluted hydrochloric acid solution is controlled at 1.0 by dripping the end point, and an activated titanium lithium ion sieve is obtained; pumping the lithium precipitation mother liquor into an ion exchange tank, cooling to 55 ℃, and sieving the ion sieve by m (ion Screen) ：m (lithium precipitation mother liquor) Immersing in lithium precipitation mother liquor in the ratio of 1:8, and after observing that the PH value of the lithium precipitation mother liquor is stable, extracting lithium to finish taking out the lithium ion sieve; sieving the ion with m (ion Screen) ：m (deionized water) The ratio =2:1 was immersed in deionized water at 50 ℃, and +.>And (3) dropwise adding a dilute hydrochloric acid solution, controlling the pH value at 0.5 by a terminal point, and taking out the titanium lithium ion sieve after the pH is stable and unchanged, so as to obtain a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve, wherein the lithium ion concentration of the lithium-rich solution is 12.7g/L.
Example 2
Mixing titanium lithium compound with deionized water according to m (lithiate) ：m (deionized water) Mixing the materials in a ratio of (1:2), and uniformly stirring to prepare slurry; sanding the slurry with 0.6-0.8 mu m zirconium beads, and spray drying to obtain D 50 Titanium-based lithiated powder=761 nm; mixing titanium lithium compound powder with PE resin powder, a dispersing auxiliary agent, a pore-forming agent and a crosslinking agent according to a mass ratio of 6:2.5:0.2:1:0.3, mixing evenly, and then compacting to prepare a titanium lithium compound plastic sheet with the thickness of 1.5 mm; the plastic sheet is divided into m parts (Plastic sheet) ：m (deionized water) =1:1 immersed in deionized water at 65 ℃, to which deionized water was slowly addedThe pH value of the diluted hydrochloric acid solution is controlled at 2.0 by dripping the end point, and an activated titanium lithium ion sieve is obtained; pumping the lithium precipitation mother liquor into an ion exchange tank, cooling to 75 ℃, and sieving the ion sieve by m (ion Screen) ：m (lithium precipitation mother liquor) Immersing the lithium ion sieve in lithium precipitation mother liquor in a ratio of (1:12), and after observing that the PH value of the lithium precipitation mother liquor is stable, extracting lithium to finish taking out the lithium ion sieve; sieving the ion with m (ion Screen) ：m (deionized water) The ratio =2:1 was immersed in deionized water at 65 ℃, and +.>And (3) dropwise adding a dilute hydrochloric acid solution, controlling the pH value at 1.5 by a terminal point, and taking out the titanium lithium ion sieve after the pH is stable and unchanged, so as to obtain a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve, wherein the lithium ion concentration of the lithium-rich solution is 12.5g/L.
Example 3
Mixing titanium lithium compound with deionized water according to m (lithiate) ：m (deionized water) Mixing the materials in a ratio of (1:2), and uniformly stirring to prepare slurry; sanding the slurry with 0.6-0.8 mu m zirconium beads, and spray drying to obtain D 50 Titanium-based lithiated powder of 582 nm; mixing titanium lithium compound powder with PE resin powder, a dispersing auxiliary agent, a pore-forming agent and a crosslinking agent according to a mass ratio of 6:2.5:0.2:1:0.3 mixingAfter uniform compression molding, a titanium lithium plastic sheet with the thickness of 1.0mm is prepared; the plastic sheet is divided into m parts (Plastic sheet) ：m (deionized water) =1:1 immersed in deionized water at 60 ℃, to which deionized water was slowly addedThe pH value of the diluted hydrochloric acid solution is controlled at 1.0 by dripping the end point, and an activated titanium lithium ion sieve is obtained; pumping the lithium precipitation mother liquor into an ion exchange tank, cooling to 60 ℃, and sieving the ion sieve by m (ion Screen) ：m (lithium precipitation mother liquor) Immersing in lithium precipitation mother liquor in a ratio of (1:10), and after observing that the PH value of the lithium precipitation mother liquor is stable, extracting lithium to finish taking out the lithium ion sieve; sieving the ion with m (ion Screen) ：m (deionized water) The ratio =2:1 was immersed in deionized water at 60 ℃, and +.>And (3) dropwise adding a dilute hydrochloric acid solution, controlling the pH value at 1.0 at the end point, and taking out the titanium lithium ion sieve after the pH is stable and unchanged, so as to obtain a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve, wherein the lithium ion concentration of the lithium-rich solution is 13.8g/L.
Part of the results of the procedure of the examples were examined, wherein the ion concentration was Agilent ICP-OES detection.
Table 1: partial detection data of example 1
Table 2: partial detection data of example 2
Table 3: partial detection data of example 3
Claims (7)
1. The method for concentrating and recycling lithium precipitation mother liquor in lithium carbonate production is characterized by comprising the following steps of:
(1) Preparing a titanium lithium ion sieve:
a. mixing titanium lithium compound with deionized water, and stirring to prepare slurry;
in the step a, the titanium lithium compound has a molecular formula of Li 2 TiO 3 The mass fraction of the effective components of the structural compound is not less than 99%, and the mass fraction of the screen residue is not more than 0.01% of 25 μm; titanium lithium compound and deionized water according to m (lithiate) ：m (deionized water) Mixing =1:2;
b. performing sanding treatment on the slurry by using zirconium beads, and performing spray drying on the sanded slurry to obtain titanium lithium compound powder meeting the requirements, wherein 0.6-0.8 mu m zirconium beads are selected; the grain diameter of the titanium lithium compound powder is controlled to be less than or equal to 300nm and less than or equal to D 50 ≤800nm；
c. Mixing titanium lithium compound powder with PE resin powder, a dispersing auxiliary agent, a pore-forming agent and a cross-linking agent uniformly, and then preparing a titanium lithium compound plastic sheet with the thickness of 0.5-1.5 mm by a compression molding machine;
in the step c, the titanium lithium compound powder, PE resin powder, a dispersing auxiliary agent, a pore-forming agent and a crosslinking agent are mixed according to the mass ratio of 6:2.5:0.2:1:0.3, mixing; the pore-forming agent is inorganic carbonate, and comprises one or a mixture of sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate;
d. immersing a plastic sheet in deionized water at 50-65 ℃, slowly adding an acid solution into the deionized water, wherein the dripping end point is to control the final pH value of the mixed solution to be 1.0-2.0, and taking out the titanium lithium compound plastic sheet after the pH value is stable and unchanged, thus obtaining an activated titanium lithium ion sieve;
(2) Concentrating lithium precipitation mother liquor lithium:
e. pumping the lithium precipitation mother liquor into an ion exchange tank, and cooling to 55-75 ℃;
f. immersing the activated titanium lithium ion sieve obtained in the step (d) in lithium precipitation mother liquor, and controlling the mass ratio of the ion sieve to the lithium precipitation mother liquor to be 1: 8-1: 12, observing the pH value of the lithium precipitation mother solution, and when the pH is stable and does not change any more, completing lithium extraction and taking out the titanium lithium ion sieve;
g. immersing a titanium lithium ion sieve after lithium extraction in deionized water at 50-65 ℃, immersing the ion sieve in the deionized water according to a mass ratio of 2:1, slowly adding a dilute acid solution into the deionized water, controlling the final pH value of the mixed solution to be 0.5-1.5 at the end point of dropwise addition of ion sieve desorption, and taking out the titanium lithium ion sieve after the pH value is stable and unchanged, thus obtaining a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve; the lithium ion concentration in the lithium-rich solution after lithium removal by the ion sieve is more than 12g/L.
2. The method for concentrating and recovering lithium deposition mother liquor in lithium carbonate production according to claim 1, wherein in step d, the plastic sheet is formed by using m (plastic sheet): m (deionized water) =1:1 immersed in deionized water; the acid solution in the step d is C (H+) Hydrochloric acid or sulfuric acid solution of =0.5 mol/L.
3. The method for concentrating and recovering lithium deposition mother liquor in lithium carbonate production according to claim 1, wherein in the step d, the final pH value of the mixed liquor is controlled to be 1.5 at the activation end point of the ion sieve.
4. The method for concentrating and recycling lithium deposition mother liquor in lithium carbonate production according to claim 1, wherein in the step f, the mass ratio of the ion sieve to the lithium deposition mother liquor is controlled to be 1:10.
5. The method for concentrating and recovering lithium deposition mother liquor in lithium carbonate production according to claim 1, wherein in step g, the added dilute acid solution is C (H+) Hydrochloric acid or sulfuric acid solution of =1.0 mol/L.
6. The method for concentrating and recycling lithium deposition mother liquor in lithium carbonate production according to claim 1, wherein in step g, the end point of the dropping of the ion sieve desorption is controlled to be 1.0 of the final pH value of the mixed liquor.
7. The method for concentrating and recycling lithium deposition mother liquor in lithium carbonate production according to claim 1, wherein the thickness of the molded titanium-based lithium compound plastic sheet in the step c is 1.0mm.
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| CN111533146A (en) * | 2020-05-07 | 2020-08-14 | 四川泛宇锂能新材料科技有限公司 | Method for recovering lithium in lithium carbonate lithium precipitation mother liquor |
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| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
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