CN113149041A - Method for concentrating and recycling lithium in lithium precipitation mother liquor in lithium carbonate production - Google Patents
Method for concentrating and recycling lithium in lithium precipitation mother liquor in lithium carbonate production Download PDFInfo
- Publication number
- CN113149041A CN113149041A CN202110172876.4A CN202110172876A CN113149041A CN 113149041 A CN113149041 A CN 113149041A CN 202110172876 A CN202110172876 A CN 202110172876A CN 113149041 A CN113149041 A CN 113149041A
- Authority
- CN
- China
- Prior art keywords
- lithium
- titanium
- mother liquor
- ion sieve
- precipitation mother
- 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.)
- Granted
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 110
- 239000012452 mother liquor Substances 0.000 title claims abstract description 37
- 238000001556 precipitation Methods 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 30
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title description 3
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 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 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000000748 compression moulding Methods 0.000 claims abstract description 8
- 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
- 230000004913 activation Effects 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 33
- 238000000605 extraction Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000010413 mother solution Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 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
- 238000003795 desorption Methods 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
- 230000008859 change Effects 0.000 claims description 3
- 150000002642 lithium compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 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
- 239000006185 dispersion Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 20
- 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
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000004576 sand Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material 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
- 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
- -1 aluminum ion Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005467 ceramic manufacturing process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001514 detection method 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
- 239000003814 drug Substances 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
- 238000007654 immersion Methods 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
- 238000007689 inspection 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
- 150000002696 manganese Chemical class 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
- 239000005304 optical glass Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 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
- 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 recovering lithium in lithium precipitation mother liquor in lithium carbonate production, which comprises the steps of firstly carrying out sand grinding on a titanium lithium compound, then carrying out spray drying to obtain titanium lithium compound powder, then mixing the titanium lithium compound powder with PE resin powder, a dispersing auxiliary agent, a pore-forming agent and a cross-linking agent, carrying out compression molding after uniform mixing to obtain a titanium lithium compound plastic sheet with proper thickness, then carrying out activation treatment on the titanium lithium compound plastic sheet to obtain a titanium lithium ion sieve, immersing the activated titanium lithium ion sieve in the lithium precipitation mother liquor, extracting lithium ions from the lithium precipitation mother liquor, and desorbing the lithium ions from the lithium ion sieve by using an acid solution to obtain a lithium solution with high lithium content and a regenerated titanium 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 by controlling the solid-liquid ratio, and the lithium recovery rate is up to more than 90 percent.
Description
Technical Field
The invention relates to a method for concentrating and recovering lithium in lithium precipitation mother liquor in lithium carbonate production, in particular to a method for concentrating and recovering lithium ions in lithium precipitation mother liquor by preparing a high-selectivity high-capacity titanium lithium ion sieve.
Background
Lithium carbonate is used as a basic lithium salt of lithium, can be directly used, and can be used as a raw material to prepare various lithium salts and compounds thereof with high added values. In the production of glass, especially cathode-ray tube, heat-resistant glass, glass fiber and optical glass, lithium carbonate can not only lower the melting temperature of glass and raise the density and strength of glass, but also improve the viscosity, heat expansibility and other important properties of glass. During the ceramic manufacturing process, the proper amount of lithium carbonate is added, so that the transparency of the product can be improved, the wear resistance is improved, the expansion coefficient and the melting temperature are reduced, the fuel consumption is reduced, and the service life of the smelting furnace is prolonged.
In medicine, lithium carbonate is used as a hypnotic and tranquilizer and has become the first choice for treating mania. In the aspect of aluminum smelting industry, the carbon material containing lithium carbonate is used for replacing a common activated carbon material to be used as an anode, the overpotential of the anode can be reduced, and electricity can be saved by 300-600 kW.h per ton of aluminum produced. In the battery field, 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 is also widely used in the industries of lubricants, rechargeable batteries, air conditioners and the like.
The conventional lithium carbonate production process is characterized in that after the enriched lithium salt solution is subjected to impurity removal, excess sodium carbonate is added into the lithium salt solution to form lithium carbonate precipitate by the characteristic that lithium carbonate is slightly soluble in water and the solubility of lithium carbonate is reduced along with the increase of the temperature, the solution is heated to more than 90 ℃ to improve the yield, and solid-liquid separation is carried out to obtain solid lithium carbonate. Because a large amount of sodium carbonate is used in the production process, when lithium carbonate precipitates are formed, part of sodium ions are inevitably carried, and therefore, a plurality of high-temperature centrifugal water washing procedures are needed to remove the sodium ions from the solid lithium carbonate obtained after solid-liquid separation. The liquid obtained by solid-liquid separation and the washing liquid obtained by water washing both contain a large amount of lithium ions and sodium ions, and the concentration of the sodium ions is generally several tens times that of the lithium ions.
This portion of the lithium precipitation mother liquor and the wash liquor, if discharged directly, results in a significant lithium loss. If the conventional high-temperature concentration and recovery method is adopted, the energy consumption is high, the production cost is high, and a large amount of sodium salt is also saturated and precipitated while the lithium carbonate is precipitated. Due to the characteristics of strong basicity and high temperature of the lithium precipitation mother liquor, an electro-osmosis membrane and an aluminum lithium ion sieve which are adopted in the conventional lithium extraction cannot be used in the environment. When the lithium ion sieve of manganese series is used for removing lithium, the dissolution loss phenomenon exists, and 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, and a method for concentrating and recovering lithium in a lithium precipitation mother solution.
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. carrying out sanding treatment on the slurry by using zirconium beads, and carrying out spray drying on the sanded slurry to obtain titanium lithium compound powder;
c. mixing the titanium lithium compound powder with PE resin powder, a dispersing aid, a pore-forming agent and a cross-linking agent according to a certain proportion, uniformly mixing, and preparing a titanium lithium compound plastic sheet with the thickness of 0.5-1.5 mm by a compression molding machine;
d. immersing the plastic sheet in deionized water, slowly adding an acid solution into the deionized water, dropwise adding an end point to control the pH value to be 1.0-2.0, and taking out the titanium lithium compound plastic sheet after the pH value is stable 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-based lithium ion sieve obtained in the step (d) in lithium precipitation mother liquor, observing the pH value of the lithium precipitation mother liquor, finishing lithium extraction when the pH value is stable and does not change any more, and taking out the titanium-based lithium ion sieve;
g. immersing the titanium lithium ion sieve after lithium extraction in deionized water, slowly adding a dilute acid solution into the deionized water, dropwise adding the dilute acid solution until the pH value is controlled to be 0.5-1.5, and taking out the titanium lithium ion sieve after the pH value is stable to obtain a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve.
Wherein the titanium lithium compound in step a has a molecular formula of Li2TiO3The mass fraction of the effective components of the compound with the structure is not less than 99 percent, and the mass fraction of the residue on sieve, 25 mu m, is not more than 0.01 percent. Titanium-based lithium compound and deionized water in m(lithiated compound)：m(deionized water)Mixing was performed at 1: 2.
In the step b, after the zirconium bead material with the particle size of 0.6-0.8 mu m is selected for sanding treatment, a spray drying nozzle with a proper pore diameter is selected for obtaining the titanium lithium compound powder with the required particle size, and the particle size D is controlled50D is less than or equal to 300nm50≤800nm。
In the step c, the mixing mass ratio of the titanium lithium compound to the PE resin powder, the dispersing aid, 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 more of sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate, and the function of the pore-forming agent is to react with acid to generate soluble salt in the subsequent activation step, so that the plastic sheet generates a porous structure and the lithium extraction efficiency is improved.
In step c, the thickness of the titanium lithium compound plastic sheet which is formed by the compression molding machine is 0.5 mm-1.5 mm, and the preferred thickness is 1.0 mm.
In step d, the acid solution is
The final pH value of the mixed solution is controlled to be 1.0-2.0, and the pH value is preferably 1.5. Plastic sheet of m(Plastic sheet)：m(deionized water)Immersing the product 1:1 in deionized water at 50-65 ℃.
In the step e, the lithium precipitation mother liquor needs to be cooled to 55-75 ℃ for use, plastic particles can be softened at an excessively high temperature, the lithium extraction efficiency and the recycling frequency of the ion sieve are affected, and the lithium extraction efficiency is affected at an excessively low temperature.
In the step f, the proportion of the ion sieve to the lithium deposition mother liquor is controlled as follows by mass ratio: 8-1: 12, preferably in a ratio of 1: 10.
In step f, the end point of lithium extraction exchange is to observe that the pH value is stable and does not change. The lithium extraction mechanism of the titanium ion sieve is H+And Li+An exchange process of absorbing Li during lithium extraction+Release of H+This results in a decrease in pH, which no longer changes when 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 a later lithium removal solution can be improved, and lithium ions can be released to the maximum extent. The reaction temperature is adjusted to 50-65 ℃, so that the desorption speed can be improved.
In step g, the acid solution is
The final desorption end point of the ion sieve is that the final pH value of the mixed solution is controlled to be 0.5-1.5, and the pH value is preferably 1.0.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) compared with the conventional lithium extraction process and the inapplicability of materials in lithium precipitation mother liquor, the method adopts the titanium lithium ion sieve as a lithium extraction means, can improve the yield by about 30 percent on the existing factory production scale, and greatly improves the factory benefit.
(2) Through many years of intensive research, the inventor improves the compression molding sheet-making formula, on one hand, the plasticity of a plastic sheet is increased, the cycle service life is prolonged, no dissolution loss and pulverization are generated in the using 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 lithium-rich solution 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 removal are carried out in a mode of immersing the plastic sheet, the equipment process flow is simple, the industrial production cost is low, and the large-area popularization is facilitated.
(4) Compared with a manganese ion sieve and an aluminum ion sieve, the titanium lithium ion sieve prepared by the invention has higher adsorption capacity, and the lithium ion concentration in the lithium-rich solution after lithium removal is more than 12 g/L.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
Titanium lithium compound and deionized water are added according to m(lithiated compound)：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 μm zirconium beads, and spray drying to obtain D50347nm titanium-based lithium compound powder; mixing the titanium lithium compound powder, PE resin powder, a dispersing aid, a pore-forming agent and a cross-linking agent according to a mass ratio of 6: 2.5: 0.2: 1: 0.3, uniformly mixing, and then performing compression molding to prepare a titanium lithium compound plastic sheet with the thickness of 0.5 mm; the plastic sheet is divided by m(Plastic sheet)：m(deionized water)1:1 was immersed in 50 ℃ deionized water and slowly added to the deionized water
Dilute hydrochloric acid solution, dropwise addingControlling the pH value to be 1.0 at the end point to obtain the activated titanium lithium ion sieve; pumping the lithium deposition mother liquor into an ion exchange tank, cooling to 55 ℃, and sieving with an ion sieve of m(ion sieve)：m(lithium mother liquor)Immersing the mother solution in a ratio of 1:8 in the lithium precipitation mother solution, and extracting lithium after observing that the pH value of the lithium precipitation mother solution is stable and unchanged; sieving the ion with m(ion sieve)：m(deionized water)Immersed in deionized water at 50 ℃ in a ratio of 2:1, slowly added to the deionized water
And (3) a dilute hydrochloric acid solution is dripped, the pH value is controlled to be 0.5 at the end point, the titanium lithium ion sieve is taken out after the pH value is stable and unchanged, and a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve are obtained, wherein the lithium ion concentration of the lithium-rich solution is 12.7 g/L.
Example 2
Titanium lithium compound and deionized water are added according to m(lithiated compound)：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 μm zirconium beads, and spray drying to obtain D50761nm titanium-based lithiated powder; mixing the titanium lithium compound powder, PE resin powder, a dispersing aid, a pore-forming agent and a cross-linking agent according to a mass ratio of 6: 2.5: 0.2: 1: 0.3, uniformly mixing, and then performing compression molding to prepare a titanium lithium compound plastic sheet with the thickness of 1.5 mm; the plastic sheet is divided by m(Plastic sheet)：m(deionized water)1:1 was immersed in 65 ℃ deionized water and slowly added to the deionized water
A dilute hydrochloric acid solution is dripped into the solution, and the pH value is controlled to be 2.0 at the end point, so that the activated titanium-based lithium ion sieve is obtained; pumping the lithium deposition mother liquor into an ion exchange tank, cooling to 75 ℃, and sieving with an ion sieve of m(ion sieve)：m(lithium mother liquor)Immersing the mother solution in a ratio of 1:12 in lithium precipitation mother solution, and taking out the lithium ion sieve after lithium extraction is finished after the pH value of the lithium precipitation mother solution is observed to be stable and unchanged; sieving the ion with m(ion sieve)：m(deionized water)Immersion in deionized water at 65 ℃ in a ratio of 2:1Slowly adding into deionized water
And (3) a dilute hydrochloric acid solution is dripped, the pH value is controlled to be 1.5 at the end point, the titanium lithium ion sieve is taken out after the pH value is stable and unchanged, and a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve are obtained, wherein the lithium ion concentration of the lithium-rich solution is 12.5 g/L.
Example 3
Titanium lithium compound and deionized water are added according to m(lithiated compound)：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 μm zirconium beads, and spray drying to obtain D50582nm titanium-based lithiated powder; mixing the titanium lithium compound powder, PE resin powder, a dispersing aid, a pore-forming agent and a cross-linking agent according to a mass ratio of 6: 2.5: 0.2: 1: 0.3, uniformly mixing, and then performing compression molding to prepare a titanium lithium compound plastic sheet with the thickness of 1.0 mm; the plastic sheet is divided by m(Plastic sheet)：m(deionized water)1:1 was immersed in deionized water at 60 ℃ and slowly added to the deionized water
A dilute hydrochloric acid solution is dripped into the solution, and the pH value is controlled to be 1.0 at the end point, so that the activated titanium-based lithium ion sieve is obtained; pumping the lithium deposition mother liquor into an ion exchange tank, cooling to 60 ℃, and sieving with an ion sieve of m(ion sieve)：m(lithium mother liquor)Immersing the lithium ion sieve into the lithium precipitation mother liquor at a ratio of 1:10, and taking out the lithium ion sieve after lithium extraction is finished after the pH value of the lithium precipitation mother liquor is observed to be stable and unchanged; sieving the ion with m(ion sieve)：m(deionized water)Immersed in deionized water at 60 ℃ in a ratio of 2:1, slowly added to the deionized water
And (3) a dilute hydrochloric acid solution is dripped, the pH value is controlled to be 1.0 at the end point, the titanium lithium ion sieve is taken out after the pH value is stable and unchanged, and a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve are obtained, wherein the lithium ion concentration of the lithium-rich solution is 13.8 g/L.
And detecting partial results in the process of the embodiment, wherein the ion concentration is an Agilent ICP-OES detection result.
Table 1: partial examination data of example 1
Table 2: partial examination data of example 2
Table 3: partial inspection data of example 3
Claims (10)
1. A method for concentrating and recovering lithium in lithium precipitation mother liquor in lithium carbonate production is characterized by comprising the following steps:
(1) preparing a titanium lithium ion sieve:
a. mixing titanium lithium compound with deionized water, and stirring to prepare slurry;
b. sanding the slurry by using zirconium beads, and spray-drying the sanded slurry to obtain titanium lithium compound powder meeting the requirements;
c. mixing titanium lithium compound powder with PE resin powder, a dispersing aid, a pore-forming agent and a cross-linking agent, uniformly mixing, and preparing a titanium lithium compound plastic sheet with the thickness of 0.5-1.5 mm by a compression molding machine;
d. immersing the plastic sheet in deionized water at 50-65 ℃, slowly adding an acid solution into the deionized water, dropwise adding the acid solution at the end point of controlling 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 to obtain the activated titanium lithium ion sieve;
(2) and (3) concentrating lithium in the lithium precipitation mother liquor:
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 a lithium precipitation mother solution, and controlling the mass ratio of the ion sieve to the lithium precipitation mother solution to be 1: 8-1: 12, observing the pH value of the lithium precipitation mother liquor, finishing lithium extraction when the pH value is stable and does not change any more, and taking out the titanium lithium ion sieve;
g. immersing the titanium lithium ion sieve after lithium extraction in deionized water at 50-65 ℃, 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 dropping end point of the desorption of the ion sieve, and taking out the titanium lithium ion sieve after the pH value is stable, thereby obtaining a lithium-rich solution with high lithium content and a regenerated titanium lithium ion sieve.
2. The method for concentrating and recovering lithium in lithium precipitation mother liquor in lithium carbonate production as claimed in claim 1, wherein in step a, the titanium-based lithiated compound is represented by the formula of Li2TiO3The mass fraction of the effective components of the compound with the structure is not less than 99 percent, and the mass fraction of the residue on sieve, 25 mu m, is not more than 0.01 percent; titanium-based lithium compound and deionized water in m(lithiated compound)：m(deionized water)Mixing was performed at 1: 2.
3. The method for concentrating and recovering lithium in the lithium precipitation mother liquor in lithium carbonate production according to claim 1, wherein in the step b, zirconium beads with the diameter of 0.6-0.8 μm are selected; the required titanium lithium compound powder has the grain diameter controlled to be D which is less than or equal to 300nm50≤800nm。
4. The method for concentrating and recovering lithium in lithium precipitation mother liquor in lithium carbonate production according to claim 1, wherein in the step c, the titanium-based lithium powder, the PE resin powder, the dispersion aid, the pore-forming agent and the cross-linking agent are mixed according to a mass ratio of 6: 2.5: 0.2: 1: 0.3, mixing; the thickness of the compression-molded titanium lithium compound plastic sheet is 1.0 mm.
5. The method for concentrating and recovering lithium in the lithium precipitation mother liquor in the lithium carbonate production as claimed in claim 1, wherein in the step c, the pore-forming agent is an inorganic carbonate containing one or a mixture of sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate.
6. The method for concentrating and recovering lithium in the lithium precipitation mother liquor in lithium carbonate production according to claim 1, wherein in the step d, the plastic sheet is in a ratio of m (plastic sheet): immersing m (deionized water) ═ 1:1 in deionized water; the acid solution is C(H+)0.5mol/L hydrochloric acid or sulfuric acid solution.
7. The method for concentrating and recovering lithium in the lithium precipitation mother liquor in the lithium carbonate production as claimed in claim 1, wherein in the step d, the final point of activation of the ion sieve is to control the final pH value of the mixed liquor to be 1.5.
8. The method for concentrating and recovering lithium in the lithium precipitation mother liquor in the lithium carbonate production as claimed in claim 1, wherein in the step f, the ratio of the ion sieve to the lithium precipitation mother liquor is controlled to be 1:10 by mass.
9. The method for concentrating and recovering lithium in lithium precipitation mother liquor in lithium carbonate production according to claim 1, wherein in the step g, the ion sieve is immersed in deionized water according to the mass ratio of 2:1, and the acid solution C is added(H+)1.0mol/L hydrochloric acid or sulfuric acid solution.
10. The method for concentrating and recovering lithium in the lithium precipitation mother liquor in the lithium carbonate production as claimed in claim 1, wherein in the step g, the desorption end point of the ion sieve is to control the final pH value of the mixed liquor to be 1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110172876.4A CN113149041B (en) | 2021-02-08 | 2021-02-08 | Method for concentrating and recycling lithium precipitation mother liquor lithium in lithium carbonate production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110172876.4A CN113149041B (en) | 2021-02-08 | 2021-02-08 | Method for concentrating and recycling lithium precipitation mother liquor lithium in lithium carbonate production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113149041A true CN113149041A (en) | 2021-07-23 |
| CN113149041B CN113149041B (en) | 2023-12-19 |
Family
ID=76882900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110172876.4A Active CN113149041B (en) | 2021-02-08 | 2021-02-08 | Method for concentrating and recycling lithium precipitation mother liquor lithium in lithium carbonate production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113149041B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114655970A (en) * | 2022-03-31 | 2022-06-24 | 神华准能资源综合开发有限公司 | Method for preparing lithium carbonate from scale evaporation mother liquor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722341A (en) * | 2017-04-25 | 2018-11-02 | 比亚迪股份有限公司 | Lithium adsorbent composite particles and preparation method thereof |
| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
| 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 |
-
2021
- 2021-02-08 CN CN202110172876.4A patent/CN113149041B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722341A (en) * | 2017-04-25 | 2018-11-02 | 比亚迪股份有限公司 | Lithium adsorbent composite particles and preparation method thereof |
| CN109225124A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of particle lithium adsorbent |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114655970A (en) * | 2022-03-31 | 2022-06-24 | 神华准能资源综合开发有限公司 | Method for preparing lithium carbonate from scale evaporation mother liquor |
| CN114655970B (en) * | 2022-03-31 | 2023-11-24 | 神华准能资源综合开发有限公司 | Method for preparing lithium carbonate from scale steaming mother liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113149041B (en) | 2023-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110783658B (en) | Ex-service power ternary lithium battery recovery demonstration process method | |
| CN102531002B (en) | Method for purifying lithium carbonate | |
| CN113061723B (en) | Method for recovering lithium from waste lithium iron phosphate batteries and preparing iron phosphate | |
| CN107653378A (en) | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery | |
| CN112142029B (en) | Method for repairing and regenerating anode material of waste lithium iron phosphate battery | |
| CN111547697B (en) | Method for repairing waste lithium iron phosphate material | |
| CN109207725A (en) | A kind of method and system recycling lithium and manganese from waste lithium manganese oxide battery | |
| CN109786739B (en) | Method for recycling lithium battery positive electrode material through molten salt assisted carbon thermal reduction | |
| CN106785166A (en) | The method that lithium prepares battery-level lithium carbonate is reclaimed in a kind of old and useless battery from LiFePO 4 | |
| CN113072052B (en) | Waste lithium iron phosphate lithium supplement repair method and application | |
| CN106916956A (en) | A kind of method that solventing-out process reclaims valuable metal and recycling in LiFePO4 waste material | |
| CN110190351B (en) | Regeneration method of waste lithium cobaltate electrode material | |
| WO2023024593A1 (en) | Method for recovering mixed waste of lithium nickel cobalt manganate and lithium iron phosphate | |
| CN116216674A (en) | Method for obtaining battery-grade lithium phosphate from waste lithium iron phosphate battery anode material | |
| Chen et al. | Hydrometallurgical processes for valuable metals recycling from spent lithium-ion batteries | |
| CN113149041B (en) | Method for concentrating and recycling lithium precipitation mother liquor lithium in lithium carbonate production | |
| CN108751234A (en) | A kind of method of purification of lithium fluoride | |
| CN111574219B (en) | Preparation method of photocatalytic lithium ferrate-titanium oxide composite block and composite block | |
| CN113363564A (en) | Lithium lanthanum zirconium tantalum oxygen solid electrolyte and preparation method and application thereof | |
| CN116375059B (en) | Technology for preparing lithium carbonate by recycling waste lithium iron phosphate battery through one-step method | |
| WO2024060547A1 (en) | Waste ternary positive electrode material reclaiming method | |
| WO2024055510A1 (en) | Method for preparing lithium iron phosphate from nickel-rion alloy and use thereof | |
| CN107640779A (en) | Spodumene produces lithium carbonate technique | |
| CN110713197A (en) | Method for recovering lithium salt from mother liquor generated in preparation of lithium iron phosphate by hydrothermal method | |
| CN113816354A (en) | Method for preparing iron phosphate by using wastes in titanium dioxide production process |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |