CN116240401A - Method for extracting rare-earth element lithium from Bayer process sodium aluminate solution - Google Patents
Method for extracting rare-earth element lithium from Bayer process sodium aluminate solution Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 104
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004131 Bayer process Methods 0.000 title claims abstract description 33
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001388 sodium aluminate Inorganic materials 0.000 title claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 6
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 20
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 claims abstract description 15
- 229940071264 lithium citrate Drugs 0.000 claims abstract description 12
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000012452 mother liquor Substances 0.000 claims abstract description 11
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 27
- 229910001919 chlorite Inorganic materials 0.000 claims description 23
- 229910052619 chlorite group Inorganic materials 0.000 claims description 23
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 23
- 238000003795 desorption Methods 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 17
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 13
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 11
- 238000005496 tempering Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 150000004645 aluminates Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 210000000582 semen Anatomy 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007385 chemical modification Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004137 mechanical activation Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 claims description 2
- 238000007725 thermal activation Methods 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims 1
- 229910003002 lithium salt Inorganic materials 0.000 claims 1
- 159000000002 lithium salts Chemical class 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000012267 brine Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002734 clay mineral Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 229910052642 spodumene Inorganic materials 0.000 abstract 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 12
- 229910000271 hectorite Inorganic materials 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 229910018068 Li 2 O Inorganic materials 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 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
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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- 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
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Abstract
According to the method, according to the low dissolution loss of layered clay minerals in sodium aluminate solution before seed precipitation, the excellent ion adsorption characteristic of the layered aluminosilicate minerals is utilized to adsorb and extract lithium dissolved in Bayer mother liquor of an alumina plant, then organic acid is used to desorb the lithium-rich layered aluminosilicate minerals, the desorbed blank layered aluminosilicate minerals can be recycled and adsorbed, and the lithium citrate solution can be directly used as a raw material for preparing a lithium battery anode. The method realizes high-efficiency, low-pollution and low-cost extraction of lithium, and provides a feasible technical route for comprehensive utilization of resources and improvement of economic benefits. The lithium production method provided by the invention is essentially different from the existing extraction method which takes spodumene and salt lake brine as raw materials, and the source of lithium is lithium resources associated with bauxite in the process of producing alumina by a Bayer process or a sintering process, which is equivalent to high added value products produced by alumina.
Description
Technical Field
The invention relates to the technical field of resources and environment, in particular to a method for extracting rare-earth element lithium from Bayer sodium aluminate solution.
Background
Lithium is a core strategic metal for new energy construction, and is the metal with the most negative potential and the greatest electrochemical equivalent, and a battery consisting of lithium has the highest specific energy, so that the lithium has unique position in the new energy field and the atomic energy industry. With the low-carbon development targets of carbon reaching peak in year 2030 and carbon neutralization in year 2060, new energy sources represented by lithium ion batteries become development trends, and market demands are gradually increased. The yield scale of the 2022 Chinese lithium battery reaches 660.8 GWh, and the yield accounts for 69% of the global lithium battery production. The market demand of the Chinese lithium battery is vigorous, but the production of the Chinese lithium carbonate mainly adopts a solid ore extraction process, and the salt lake brine extraction process is limited by factors such as difficult magnesium-lithium separation, and the like, so that the development speed is relatively slow, and the lithium resource supply becomes the biggest restriction of the development of the Chinese lithium battery industry. According to prediction, the lithium demand in China in 2030 is 70 ten thousand t, about 45-50 ten thousand t lithium is imported, and great potential safety hazards exist in the lithium resource guarantee in China. Among the amount of lithium resources that have been ascertained worldwide, south america lithium delta (bolivia, argentina, chile) accounts for 57%, followed by 10% in the united states, 8% in australia, and only 6% in china.
The lithium resources in China are mainly salt lake brine and granite pegmatite, while sedimentary rock is not generally used as a target geologic body for searching lithium, but the total amount of mineral resources of the type is huge, including bauxite, coal mine and kaolin deposit, and the method has a wide development prospect.
Li Sui, et al, "a preparation method of a lithium-adsorbing material", application number: CN 201810379023.6' introduces N element into the functional group of the adsorption material according to the activity of lithium and different characteristics of the lithium in the solution, adopts nitrogen connection, adopts sulfonic acid, phosphoric acid and carboxylic acid functional groups with exchange property, and can be easily combined with lithium ions, so that lithium is exchanged on the material, and other monovalent ions are not exchanged, thereby achieving the purpose of enrichment and purification.
Ma Haijun et al, "method for extracting lithium carbonate from sodium aluminate solution in alumina plant", application number: CN201710883825.6 "adding aluminium hydroxide seed crystal into lithium-rich seminal fluid of alumina factory to precipitate lithium, separating high-lithium primary aluminium hydroxide (aluminium hydroxide) from seminal fluid after precipitating lithium, countercurrent washing filter cake with hot water (generally countercurrent washing filter cake with 1-3 times of hot water for 2-3 times) to obtain high-lithium primary aluminium hydroxide, leaching the high-lithium primary aluminium hydroxide washed with hot water by hydrothermal method to transfer lithium into solution again, separating slurry again to obtain hydrated alumina and lithium-containing leaching solution after leaching, neutralizing lithium-containing leaching solution with inorganic acid, and adding saturated sodium carbonate aqueous solution to crystallize lithium carbonate.
Ji Lijuan et al, "a method for reducing lithium content in alumina products, application number: CN201811609306.1 "adsorbs lithium in a sodium aluminate solution by adding an aluminum-containing compound as an adsorbent to the sodium aluminate solution containing lithium; the lithium in the solution is promoted to be separated out by controlling the reaction temperature and stirring time of the solution; filtering to obtain a lithium-rich filter cake and filtrate; the filtrate enters the subsequent process for preparing the alumina product.
The production scale of alumina in China is huge, the lithium resources associated with bauxite are not reasonably utilized, and Li is taken away annually through metallurgical-grade alumina 2 O is as high as 1.5-2 ten thousand tons, and the lithium-rich aluminum oxide can reduce the current efficiency and increase the energy consumption in the aluminum electrolysis process, so that the working condition of the electrolytic tank is deteriorated. The existing research on comprehensive benefit of byproduct lithium resources of an alumina production system is not reasonable enough, the defects of the related technology are large, and the associated lithium resources of bauxite are not well solved.
Disclosure of Invention
In order to better utilize byproduct lithium resources of an alumina production system, the invention provides a method for extracting scattered element lithium from a Bayer sodium aluminate solution, namely, a dihedral layered aluminosilicate mineral with a 2:1 unit structure layer is used as a circulating adsorbent, citric acid is used as a desorbing agent, and the efficient extraction of lithium is realized on the basis of not changing the original Bayer process production flow. The technical scheme for realizing the invention is carried out according to the following steps:
(1) Activating (mechanical activation, thermal activation and chemical modification) the layered aluminosilicate mineral, wherein the activated mineral is used as an adsorbent for dispersing elements in the sodium aluminate solution;
(2) Adding activated aluminosilicate minerals (montmorillonite, chlorite, pyrophyllite and illite) into sodium aluminate semen in the Bayer process to adsorb lithium, controlling the adding amount of the minerals to be 1.5-15 g/L, controlling the reaction temperature to be 65-90 ℃ and the reaction time to be 0.5-6 h, carrying out liquid-solid separation after full reaction, continuously entering a seed precipitation process from the separated Bayer mother liquor, and further treating a filter cake to extract lithium;
(3) Desorbing the hectorite-rich material obtained in the previous step by adopting organic acid (citric acid);
(4) Returning the desorbed blank montmorillonite to the adsorption process for recycling;
(5) The lithium citrate solution obtained in the desorption process is directly used as a raw material for preparing the anode of the lithium battery after impurity removal and tempering.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
(1) The layered aluminosilicate mineral has low reactivity, stable structure and excellent ion adsorption property in Bayer process mother liquor before seed precipitation, and meanwhile, the aluminosilicate mineral does not have adverse effect on the mother liquor components, so that the efficient adsorption of lithium can be realized;
(2) The process steps are simple, the lithium extraction rate is high and can reach 90-95%, the mother liquor after lithium extraction is purified, the lithium content in the produced aluminum oxide product can be reduced to 0.05%, and the method can better meet the component requirements of an aluminum electrolysis process;
(3) The desorption effect of the citric acid is excellent, the desorption rate can reach 88%, the desorbed aluminosilicate mineral can be recycled, the high peak adsorption capacity can be maintained, and the adsorption capacity still has 60-110 mmol/100g after 5 times of cyclic adsorption.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Sodium bayer process aluminate solution concentration Na 2 O（N k ）=160g/L，αk=1.5，Li 2 O concentration is 1g/L; the liquid-solid ratio is 200:1, the temperature is 90 ℃, 1.5g of montmorillonite is added, stirring time is 360 minutes, after the completion, the hectorite-rich liquid is obtained through filtration, and the filtrate returns to the Bayer process flow. The detection shows that the extraction rate of lithium in the sodium aluminate solution is 92.80 percent.
And (3) after the hectorite is dried, desorbing by adopting a citric acid solution under the following desorption conditions: and adding 1g of hectorite with the concentration of 0.5 mol/L and the liquid-solid ratio of 20:1, reacting for 60 minutes, then carrying out liquid-solid separation, wherein the desorption rate is 83.25%, returning the desorbed blank montmorillonite to the adsorption process for recycling, and directly preparing the lithium citrate solution for lithium battery anode after impurity removal and tempering.
Example 2
Sodium bayer process aluminate solution concentration Na 2 O（N k ）=160g/L，αk=1.5，Li 2 O concentration is 1g/L; the liquid-solid ratio is 200:1, the temperature is 80 ℃, 1.5g of montmorillonite is added, stirring time is 360 minutes, after the completion, the hectorite-rich liquid is obtained through filtration, and the filtrate returns to the Bayer process flow. The detection shows that the extraction rate of lithium metal in the sodium aluminate solution is 94.50%.
And (3) after the hectorite is dried, desorbing by adopting a citric acid solution under the following desorption conditions: and (3) adding 1g of hectorite with a liquid-solid ratio of 20:1 at the temperature of 25 ℃ and the concentration of 0.5 mol/L, reacting for 60 minutes, enabling the desorption rate to reach 84.63%, then carrying out liquid-solid separation, returning the desorbed blank montmorillonite to an adsorption process for recycling, and directly preparing the lithium citrate solution after impurity removal and tempering.
Example 3
Sodium bayer process aluminate solution concentration Na 2 O（N k ）=160g/L，αk=1.5，Li 2 O concentration is 1g/L; 2g of montmorillonite is added into the solution with the liquid-solid ratio of 200:1 and the temperature of 80 ℃ and stirred for 360 minutes, and after the completion, the hectorite-rich solution is obtained through filtration, and the filtrate returns to the Bayer process flow. The detection shows that the extraction rate of lithium metal in the sodium aluminate solution is 91.09%.
And (3) after the hectorite is dried, desorbing by adopting a citric acid solution under the following desorption conditions: and (3) adding 1g of hectorite with a liquid-solid ratio of 20:1 at the temperature of 25 ℃ and the concentration of 1 mol/L, reacting for 60 minutes, separating liquid and solid until the desorption rate reaches 85%, returning the desorbed blank montmorillonite to an adsorption process for recycling, and directly preparing the lithium citrate solution after impurity removal and tempering.
Example 4
Sodium bayer process aluminate solution concentration Na 2 O（N k ）=160g/L，αk=1.5，Li 2 O concentration is 1g/L; the liquid-solid ratio is 400:1, the temperature is 80 ℃, 1.5g of montmorillonite is added, stirring time is 360 minutes, after the completion, the hectorite-rich liquid is obtained through filtration, and the filtrate returns to the Bayer process flow. The detection shows that the extraction rate of lithium metal in the sodium aluminate solution is 93.28 percent.
And (3) after the hectorite is dried, desorbing by adopting a citric acid solution under the following desorption conditions: and (3) adding 1g of lithium-rich montmorillonite at the temperature of 25 ℃ and the concentration of 1 mol/L, wherein the liquid-solid ratio is 1:1, reacting for 60 minutes, and performing liquid-solid separation until the desorption rate reaches 87.64%, wherein the desorbed blank montmorillonite is returned to the adsorption process for recycling, and the lithium citrate solution can be directly used for preparing the anode of the lithium battery after impurity removal and tempering.
Example 5
Concentration of Bayer process mother liquor Na 2 O（N k ）=165g/L，αk=1.45，Li 2 O concentration is 1g/L; the liquid-solid ratio is 200:1, the temperature is 90 ℃, 1.5g of chlorite is added, stirring time is 360 minutes, after the completion, the lithium-rich chlorite is obtained through filtration, and the filtrate returns to the Bayer process flow. The detection shows that the extraction rate of lithium metal in the sodium aluminate solution is 85.80%.
And (3) after drying the lithium-rich chlorite, desorbing by adopting a citric acid solution under the following desorption conditions: and (3) adding 1g of lithium-rich chlorite at the temperature of 25 ℃ and the concentration of 0.5 mol/L in a liquid-solid ratio of 20:1, reacting for 60 minutes, then carrying out liquid-solid separation, returning the desorbed blank chlorite to an adsorption process for recycling, and directly preparing the anode of the lithium battery after impurity removal and tempering of the lithium citrate solution.
Example 6
Concentration of Bayer process mother liquor Na 2 O（N k ）=165g/L，αk=1.45，Li 2 O concentration is 1g/L; the liquid-solid ratio is 200:1, the temperature is 80 ℃, 1.5g of chlorite is added, stirring time is 360 minutes, after the completion, the lithium-rich chlorite is obtained through filtration, and the filtrate returns to the Bayer process flow. The detection shows that the extraction rate of lithium metal in the sodium aluminate solution is 90.50%.
And (3) after drying the lithium-rich chlorite, desorbing by adopting a citric acid solution under the following desorption conditions: and (3) adding 1g of lithium-rich chlorite at the temperature of 25 ℃ and the concentration of 0.5 mol/L in a liquid-solid ratio of 20:1, reacting for 60 minutes, enabling the desorption rate to reach 82.63%, performing liquid-solid separation, returning the desorbed blank chlorite to an adsorption process for recycling, and directly preparing the anode of the lithium battery after impurity removal and tempering of the lithium citrate solution.
Example 7
Concentration of Bayer process mother liquor Na 2 O（N k ）=165g/L，αk=1.45，Li 2 O concentration is 1g/L; the liquid-solid ratio is 200:1, the temperature is 80 ℃, 2g of chlorite is added, stirring time is 360 minutes, after the completion, the lithium-rich chlorite is obtained through filtration, and the filtrate returns to the Bayer process flow. The detection shows that the extraction rate of lithium metal in the sodium aluminate solution is 92.43 percent.
And (3) after drying the lithium-rich chlorite, desorbing by adopting a citric acid solution under the following desorption conditions: and (3) adding 1g of lithium-rich chlorite at the temperature of 25 ℃ and the concentration of 1 mol/L, the liquid-solid ratio of 20:1, reacting for 60 minutes, wherein the desorption rate reaches 88.34%, then performing liquid-solid separation, returning the desorbed blank chlorite to the adsorption process for recycling, and directly preparing the anode of the lithium battery after impurity removal and tempering of the lithium citrate solution.
Example 8
Concentration of Bayer process mother liquor Na 2 O（N k ）=165g/L，αk=1.45，Li 2 O concentration is 1g/L; the liquid-solid ratio is 400:1, the temperature is 80 ℃, 1.5g of chlorite is added, stirring time is 360 minutes, after the completion, the lithium-rich chlorite is obtained through filtration, and the filtrate returns to the Bayer process flow. The detection shows that the extraction rate of lithium metal in the sodium aluminate solution is 94.63 percent.
And (3) after drying the lithium-rich chlorite, desorbing by adopting a citric acid solution under the following desorption conditions: and (3) adding 1g of lithium-rich chlorite at the temperature of 25 ℃ and the concentration of 1 mol/L in a liquid-solid ratio of 1:1, reacting for 60 minutes, enabling the desorption rate to reach 89.68%, then carrying out liquid-solid separation, returning the desorbed blank chlorite to an adsorption process for recycling, and directly preparing the anode of the lithium battery after impurity removal and tempering of the lithium citrate solution.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (8)
1. A method for extracting scattered element lithium from Bayer process sodium aluminate solution relates to recycling of associated scattered elements in bauxite, and comprises the following steps:
(1) Activating (mechanical activation, thermal activation and chemical modification) the layered aluminosilicate mineral, wherein the activated mineral is used as an adsorbent for dispersing elements in the sodium aluminate solution;
(2) Adding activated aluminosilicate minerals (montmorillonite, chlorite, pyrophyllite and illite) into sodium aluminate semen in the Bayer process to adsorb lithium, controlling the adding amount of the minerals to be 1.5-15 g/L, controlling the reaction temperature to be 65-90 ℃ and the reaction time to be 0.5-6 h, carrying out liquid-solid separation after full reaction, continuously entering a seed precipitation process from the separated Bayer mother liquor, and further treating a filter cake to extract lithium;
(3) Desorbing the lithium-rich layered aluminosilicate mineral obtained in the previous step by adopting organic acid (citric acid);
(4) Returning the desorbed blank layered aluminosilicate mineral to the adsorption process for recycling;
(5) The lithium citrate solution obtained in the desorption process is directly used as a raw material for preparing the anode of the lithium battery after impurity removal and tempering.
2. The method for extracting rare earth element lithium from a sodium bayer process aluminate solution according to claim 1, wherein the layered aluminosilicate mineral crystal structure is dioctahedral of a 2:1 type unit structure layer, comprising: montmorillonite, chlorite, pyrophyllite, illite, and the material has the function of separating and extracting lithium from Bayer process mother liquor.
3. The method for extracting rare-earth element lithium from sodium bayer process aluminate solution according to claim 1, wherein the lithium adsorption material is prepared by mixing a solution of sodium bayer process aluminate (55-85 ℃ and N k =140 to 170 g/L) is low in reactivity, and the structure is not changed.
4. The method for extracting scattered element lithium from Bayer process sodium aluminate solution according to claim 1, wherein the method for activating the layered aluminosilicate mineral comprises mechanical ball milling, low-temperature roasting (110-650 ℃), and salt solution modification (lithium salt and sodium salt).
5. The method for extracting scattered element lithium from Bayer process sodium aluminate solution according to claim 1, wherein the lithium adsorption material can selectively extract lithium in the solution, the mineral addition amount is 1.5-15 g/L, the reaction temperature is 65-90 ℃, and the reaction time is 0.5-6 h.
6. The method for extracting scattered element lithium from sodium bayer process aluminate solution according to claim 1, wherein the desorbent citric acid is an organic acid, and the desorption process is complexed with lithium in a lithium adsorption material to realize removal of lithium.
7. The method for extracting rare-earth element lithium from sodium bayer process aluminate solution according to claim 1, wherein the analyzed lithium adsorption material has unchanged structure and performance and can be recycled.
8. The method for extracting scattered element lithium from Bayer process sodium aluminate solution according to claim 1, wherein the lithium citrate solution obtained after the analysis is subjected to impurity removal and tempering, and is directly used as a raw material to prepare the lithium battery anode.
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