CN114751434A - Comprehensive recycling method of sedimentary lithium resource - Google Patents
Comprehensive recycling method of sedimentary lithium resource Download PDFInfo
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- CN114751434A CN114751434A CN202210470990.XA CN202210470990A CN114751434A CN 114751434 A CN114751434 A CN 114751434A CN 202210470990 A CN202210470990 A CN 202210470990A CN 114751434 A CN114751434 A CN 114751434A
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- sodium
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000047 product Substances 0.000 claims abstract description 34
- 238000002386 leaching Methods 0.000 claims abstract description 33
- 238000005188 flotation Methods 0.000 claims abstract description 28
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 28
- 239000011707 mineral Substances 0.000 claims abstract description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 22
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 20
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 17
- 239000012141 concentrate Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 230000001376 precipitating effect Effects 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 92
- 239000000243 solution Substances 0.000 claims description 59
- 238000000926 separation method Methods 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 235000010755 mineral Nutrition 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000011575 calcium Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000002893 slag Substances 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- -1 ether amine Chemical class 0.000 claims description 7
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 7
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 7
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 230000003213 activating effect Effects 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 description 13
- 230000002000 scavenging effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 229910052900 illite Inorganic materials 0.000 description 4
- 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 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 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 description 4
- 238000001556 precipitation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910018125 Al-Si Inorganic materials 0.000 description 2
- 229910018520 Al—Si Inorganic materials 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 239000010438 granite Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Abstract
The invention provides a comprehensive recycling method of a deposition type lithium resource, which comprises the following steps: crushing and grinding the sedimentary lithium ore to obtain fine-grained minerals; performing flotation on the fine-grained minerals to obtain flotation concentrate and flotation tailings, wherein the flotation concentrate is a lithium-rich product, and the flotation tailings are bauxite concentrate products; carrying out sulfuric acid curing and water leaching on the lithium-rich product to convert lithium from a solid phase into a liquid phase to obtain a lithium-containing leaching solution; purifying and decontaminating the leaching solution to obtain a final purified solution; and adding sodium carbonate into the final purification solution for reaction, precipitating a precipitate after the reaction is completed, washing and drying the precipitate to obtain the lithium carbonate. The method provided by the invention is used for treating the sedimentary lithium ore to obtain a bauxite concentrate product and a high-purity lithium carbonate product, so that the comprehensive recovery and utilization of sedimentary lithium resources are realized, the high-temperature roasting is not needed, the energy is saved, the consumption is reduced, the high-purity lithium carbonate product reaches the battery level, the battery level meets the battery quality standard requirement of the new energy industry, and the method can be applied to the manufacturing of lithium batteries in new energy automobiles.
Description
Technical Field
The invention relates to the technical field of comprehensive recovery of lithium resources, in particular to a comprehensive recovery and utilization method of a deposition type lithium resource.
Background
Lithium is the lightest metal in nature and has wide application in the traditional fields such as glass, ceramics, metallurgy industry, medicine, organic synthesis and the like. At present, China is fully promoting the transformation and upgrading of the traditional industry. The lithium is a key mineral product indispensable to the development of strategic emerging industries in the future in China, and is also called white petroleum, penetrating through ten fields of new-generation information technology industry, high-grade numerical control machines and robots, energy-saving and new-energy automobiles, electric equipment, new materials, biological medicines, high-performance medical instruments and the like. China is the first major lithium consuming country, the global lithium consumption is about 4.76 ten thousand tons in 2018, the consumption amount of China is close to 50% of the world, but the external dependence of the China lithium resource is over 80%, so that the search for a new lithium resource is urgent.
Currently, there are mainly 3 types of lithium deposits found in nature: salt lake brine type, granite pegmatite-alkali long granite type and sedimentary type. Compared with the world's main lithium resource country, China is not superior in the resource amount of the first 2 types of ore deposits, and the sedimentary lithium ore is a potential lithium resource library. The lithium content in the Chinese bauxite (rock) is in the front of various sedimentary lithium ores, and the Chinese bauxite finds that the reserves are over 50 hundred million tons, the basic reserves are over 10 hundred million tons, and the reserves of the associated lithium resources are considerable. However, China has not independently developed and utilized sedimentary lithium ore.
The document CN110042262A discloses a method for selectively leaching low-grade deposition type lithium ores, the method comprises the steps of roasting at 500-700 ℃ to obtain a mature ore, and leaching the mature ore at 20-60 ℃ by using inorganic acid to obtain a lithium-rich solution. The method has the advantages of high roasting reaction temperature and high energy consumption, meanwhile, in the method, part of silicon elements are leached into the solution, so that the subsequent impurity removal difficulty is increased, only the leaching condition of the lithium solution is considered, and no reference is made to the subsequent impurity removal and extraction.
Disclosure of Invention
The invention provides a comprehensive recycling method of sedimentary lithium resources, which can obtain qualified bauxite concentrate products and high-purity lithium carbonate products, realizes comprehensive recycling and utilization of sedimentary lithium resources, does not need high-temperature roasting, and saves energy and reduces consumption. In addition, the high-purity lithium carbonate product reaches the battery level, meets the quality standard requirement of batteries in the new energy industry, and can be applied to the manufacture of lithium batteries in new energy automobiles.
The technical scheme of the invention is realized as follows: a comprehensive recycling method of deposition type lithium resources comprises the following steps:
s1: crushing and grinding the sedimentary lithium ore to 70-80% of the granularity smaller than 0.074mm to obtain fine-grained minerals;
s2: performing flotation on the fine-grained minerals to obtain flotation concentrate and flotation tailings, wherein the flotation concentrate is a lithium-rich product, and the flotation tailings are bauxite concentrate products;
s3: carrying out sulfuric acid curing and water leaching on the lithium-rich product to convert lithium from a solid phase into a liquid phase to obtain a lithium-containing leaching solution;
s4: purifying the leachate to remove impurities, and removing impurities such as iron, aluminum, sodium and calcium to obtain a final purified solution;
s5: and (4) adding sodium carbonate into the final purified liquid obtained in the step S4, reacting at 90-100 ℃, precipitating a precipitate after complete reaction, washing and drying the precipitate to obtain lithium carbonate.
Further, in step S1, Li in the deposit-type lithium ore2The grade of O is 0.1-0.6%, Al2O3Grade of (2)>50% of Al/Si ratio>2.6。
Further, in step S3, the raw material for sulfuric acid curing is concentrated sulfuric acid with a mass concentration of 50% -80%, the curing temperature is 120-175 ℃, the curing liquid-solid ratio is 0.5-2:1, and the curing time is 20-100 min.
Further, in step S3, the water immersion temperature is normal temperature, the water immersion liquid solid ratio is 0.5-2:1, and the water immersion time is 5-30 min.
Further, in step S2, the flotation method includes: adjusting the pH value of the ore pulp to 4-6 by sulfuric acid or hydrochloric acid in the fine-grained minerals; and then adding 20-100 g/t of an activating agent, 40-100 g/t of an inhibitor and 50-150 g/t of a collecting agent, wherein the activating agent is sodium chloride or potassium chloride, the inhibitor is one or two of sodium hexametaphosphate and polyacrylamide, and the collecting agent is one or more of fatty amine, ether amine and quaternary ammonium salt.
Further, in step S4, the method for removing iron by purification includes: adding oxidant into the leaching solution to lead Fe in the leaching solution to be2+All converted into Fe3+Then adding a pH regulator to adjust the pH of the leachate to 3.5-4.0, precipitating iron, and carrying out solid-liquid separation to obtain iron slag and primary purification liquid; the oxidant is one or two of hydrogen peroxide and sodium peroxide, and the pH regulator is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate.
Further, in step S4, the method for removing aluminum by purification includes: adding a pH regulator into the primary purification liquid to regulate the pH of the leachate to 6.0-7.0, precipitating aluminum, and carrying out solid-liquid separation to obtain aluminum slag and secondary purification liquid; the pH regulator is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate solution.
Further, in step S4, the method for purifying and removing sodium includes: concentrating the secondary purified liquid to the volume ratio of 1 (8-10) to the original volume ratio, then carrying out solid-liquid separation to obtain concentrated salt and concentrated liquid, cooling the concentrated liquid to 10-20 ℃, and carrying out solid-liquid separation to obtain cooling salt and tertiary purified liquid;
further, in step S4, the method for purifying and removing calcium includes: and adding sodium carbonate into the third purified liquid, adjusting the pH value to 9.5-10.5, precipitating calcium ions in the third purified liquid in the form of calcium carbonate, and performing solid-liquid separation to obtain calcium slag and final purified liquid.
Further, in step S5, a 330g/L sodium carbonate solution with a mass concentration of 300-.
The invention has the beneficial effects that:
the method has simple process, no tailings are generated, the resource utilization rate is improved, the comprehensive recovery of the deposition type lithium resource is realized, the cooperation of crushing, grinding, flotation and sulfuric acid curing water immersion is adopted, the leaching rate of lithium reaches more than 92%, high-temperature roasting is not needed, energy is saved, consumption is reduced, the subsequent purification and impurity removal are carried out on the lithium-containing leaching solution, the removal rate of Fe is more than 99.9%, the removal rate of Al is more than 99.9%, the removal rate of Ca is more than 99%, the loss rate of lithium is very small in the whole impurity removal process, finally the precipitation rate of lithium reaches more than 84%, the purity of a lithium carbonate product reaches more than 99.5%, the lithium carbonate reaches the battery level, meets the quality standard requirement of batteries in the new energy industry, and can be applied to the manufacture of lithium batteries in new energy automobiles. The invention not only recovers lithium resources, but also aluminum resources. At present, no independently developed and utilized deposition type lithium ore exists in China, the invention realizes the technical storage increase of lithium and can relieve the external dependence of lithium resources.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a process flow diagram of the comprehensive recycling method of sedimentary lithium resources according to the present invention;
figure 2 is a process flow for flotation in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
As shown in fig. 1, a comprehensive recycling method of a deposition type lithium resource includes the following steps:
s1: crushing and grinding the sedimentary lithium ore to 70-80% of the granularity smaller than 0.074mm to obtain fine-grained minerals;
s2: performing flotation on the fine-grained minerals to obtain flotation concentrate and flotation tailings, wherein the flotation concentrate is a lithium-rich product, and the flotation tailings are bauxite concentrate products;
s3: carrying out sulfuric acid curing and water leaching on the lithium-rich product to convert lithium from a solid phase into a liquid phase to obtain a lithium-containing leaching solution;
s4: purifying the leachate to remove impurities, and removing impurities such as iron, aluminum, sodium and calcium to obtain a final purified solution;
s5: and (4) adding sodium carbonate into the final purified liquid obtained in the step S4, reacting at 90-100 ℃, precipitating a precipitate after complete reaction, washing and drying the precipitate to obtain lithium carbonate.
In step S1, Li in deposit-type lithium ore2The grade of O is 0.1-0.6%, Al2O3Grade of (2)>50% of Al/Si ratio>2.6。
In step S3, the raw material for sulfuric acid curing is concentrated sulfuric acid with mass concentration of 50% -80%, the curing temperature is 120-175 ℃, the curing liquid-solid ratio is 0.5-2:1, and the curing time is 20-100 min.
In step S3, the water immersion temperature is normal temperature, the solid ratio of the water immersion liquid is 0.5-2:1, and the water immersion time is 5-30 min.
In step S2, the flotation method includes: adjusting the pH value of the ore pulp to 4-6 by sulfuric acid or hydrochloric acid in the fine-grained minerals; and then adding 20-100 g/t of an activating agent, 40-100 g/t of an inhibitor and 50-150 g/t of a collecting agent, wherein the activating agent is sodium chloride or potassium chloride, the inhibitor is one or two of sodium hexametaphosphate and polyacrylamide, and the collecting agent is one or more of fatty amine, ether amine and quaternary ammonium salt.
In step S4, the method for removing iron by purification includes: adding oxygen to the leach solutionA chemical agent for making Fe in the leaching solution2+All converted to Fe3+Then adding a pH regulator to adjust the pH of the leachate to 3.5-4.0, precipitating iron, and carrying out solid-liquid separation to obtain iron slag and primary purification liquid; the oxidant is one or two of hydrogen peroxide and sodium peroxide, and the pH regulator is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate.
In step S4, the method for removing aluminum by purification comprises: adding a pH regulator into the primary purification liquid to regulate the pH of the leachate to 6.0-7.0, precipitating aluminum, and carrying out solid-liquid separation to obtain aluminum slag and secondary purification liquid; the pH regulator is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate solution.
In step S4, the method for purifying and removing sodium includes: and (3) concentrating the secondary purified liquid to the volume ratio of 1 (8-10) to the original volume, then carrying out solid-liquid separation to obtain concentrated salt and concentrated liquid, cooling the concentrated liquid to 10-20 ℃, and carrying out solid-liquid separation to obtain cooling salt and tertiary purified liquid.
In step S4, the method for purifying and removing calcium comprises: adding sodium carbonate into the third purified liquid, adjusting the pH value to 9.5-10.5 to separate out calcium ions in the third purified liquid in the form of calcium carbonate, and carrying out solid-liquid separation to obtain calcium slag and final purified liquid.
In the step S5, a 330g/L sodium carbonate solution with the mass concentration of 300-100 ℃ is added into the final purification solution, the reaction temperature is 90-100 ℃, the reaction time is 20-60min, the bottom is washed by using a washing solution, the washing solution is 80-95 ℃ deionized water or a saturated solution of lithium carbonate, and the ratio of the usage amount of the washing solution to the wet weight of the lithium carbonate is 1-1.5: 1.
The specific embodiment is as follows:
example 1
Li-bearing Li-deposit type Li-ore of Guizhou2O 0.13％，Al2O3 58.62％，SiO220.86 percent of the mineral composition comprises diaspore, kaolinite and illite, and lithium is mainly contained in the minerals such as kaolinite, illite and the like.
As shown in fig. 1 and 2, a comprehensive recycling method of a deposition type lithium resource is as follows:
the lithium-containing bauxite is crushed and ground into fine powder to obtain fine-grained mineral, and the content of the lithium-containing bauxite of-200 meshes in the fine-grained mineral is 70%.
Adding sulfuric acid into fine-grained minerals to adjust the pH value of ore pulp to 4, adopting a flotation process of primary roughing, primary concentrating and twice scavenging to perform separation, wherein the dosage of a medicament for the primary roughing is 20g/t of potassium chloride, 40g/t of polyacrylamide, 50g/t of dodecylamine is added, the dosage of a medicament for the primary concentrating is 20g/t of polyacrylamide, the dosage of a medicament for the primary scavenging is 25g/t of dodecylamine, and the dosage of a medicament for the secondary scavenging is 20g/t of dodecylamine, so as to obtain Al2O3Grade 64.23%, Al2O3Bauxite concentrate product with recovery rate of 75.47%, aluminum-silicon ratio of 6.72 and Li2O grade of 0.36%, Li2And the recovery rate of O is 86.18 percent of lithium-rich product.
Taking 1500g of a lithium-rich product, and mixing concentrated sulfuric acid with the mass concentration of 80% with the lithium-rich product according to the volume mass ratio of 1:1, and curing and reacting for 100min at the temperature of 175 ℃ to obtain the lithium-containing clinker. Stirring and leaching the lithium-containing clinker by using 3.0L of water, wherein the leaching temperature is 25 ℃, the leaching time is 10min, then carrying out solid-liquid separation to obtain a lithium-containing leaching solution, and adopting concentrated sulfuric acid to destroy the mineral phase structure to convert the mineral phase, so that the mineral phase is converted into a soluble salt, and the leaching rate of lithium reaches 94.64%.
Adding sufficient hydrogen peroxide into the lithium-containing leachate, adding a sodium hydroxide solution after complete reaction to adjust the pH value to 4.0, carrying out solid-liquid separation and retaining a first purified solution.
And adding a sodium hydroxide solution into the first purified liquid to adjust the pH value to 6.5, carrying out solid-liquid separation after complete reaction, and reserving the second purified liquid. In this case, the Fe removal rate was 99.95%, the Al removal rate was 99.94%, and the loss rate of lithium was small, only 1.94%.
And (3) evaporating and concentrating the second purified liquid in a boiling state until the volume is 1/8, carrying out solid-liquid separation to obtain concentrated salt and concentrated liquid, cooling the concentrated liquid to 10 ℃ while the concentrated liquid is hot, and carrying out solid-liquid separation to obtain cooled salt and third purified liquid. Drying the concentrated salt and the cooled salt to obtain anhydrous sodium sulphate meeting the standard. The loss rate of lithium in this step was 0.36%.
Adding sodium carbonate solution into the third purified solution to adjust pH to 10.5, and performing solid-liquid separation to obtain final purified solution with Ca removal rate of 99.2%.
Heating the final purification liquid to boiling, adding 300g/L sodium carbonate solution to react for 30min, performing solid-liquid separation to obtain precipitated lithium carbonate, washing with 95 ℃ deionized water according to the wet-weight mass ratio of 1:1 of the precipitate, and drying to obtain a lithium carbonate product (Li) meeting the national standard GB/T11075-20132CO399.56%), the precipitation rate of lithium reached 84.52%.
Example 2
Li-bearing deposit type lithium ore in Hexi of China2O 0.27％，Al2O3 52.87％，SiO216.87 percent, the main minerals are diaspore, kaolinite and illite, and lithium is mainly contained in minerals such as kaolinite, illite and the like.
A comprehensive recycling method of a deposition type lithium resource comprises the following steps:
the lithium-containing bauxite is crushed and ground into fine powder to obtain fine-grained mineral, and the content of the lithium-containing bauxite of-200 meshes in the fine-grained mineral is 75%. Adding sulfuric acid into fine-grained minerals to adjust the pH value of ore pulp to be 5, adopting a flotation process of one-time roughing, one-time concentrating and one-time scavenging to carry out separation, wherein the dosage of the one-time roughing medicament is 60g/t of sodium chloride, 40g/t of sodium hexametaphosphate, 75g/t of dodecylamine is added, the dosage of the one-time concentrating medicament is 20g/t of sodium hexametaphosphate, and the dosage of the one-time scavenging medicament is 25g/t of dodecylamine, so as to obtain Al2O3Grade 65.32%, Al2O3Bauxite concentrate product with recovery rate of 76.39% and Al-Si ratio of 8.7 and Li2O grade of 0.65%, Li2And the recovery rate of O is 91.89 percent.
Taking 1500g of a lithium-rich product, and mixing concentrated sulfuric acid with the mass concentration of 75% and the lithium-rich product according to the volume mass ratio of 2:1, curing and reacting for 90min at the temperature of 150 ℃ to obtain the lithium-containing clinker. Stirring and leaching the lithium-containing clinker by using 2.0L of water, wherein the leaching temperature is 25 ℃, the leaching time is 30min, then carrying out solid-liquid separation to obtain a lithium-containing leaching solution, and the leaching rate of lithium reaches 93.58%.
Adding sufficient sodium peroxide into the lithium-containing leachate, adding a sodium hydroxide solution after complete reaction to adjust the pH to 3.9, carrying out solid-liquid separation and retaining a first purified solution.
And adding a sodium hydroxide solution into the first purified liquid to adjust the pH value to 6.8, carrying out solid-liquid separation after complete reaction, and reserving the second purified liquid. In this case, the Fe removal rate was 99.98%, the Al removal rate was 99.95%, and the loss rate of lithium was small, only 1.88%.
And (3) carrying out solid-liquid separation on the second filtrate in a boiling state when the second filtrate is evaporated and concentrated to the original volume of 1/10 to obtain concentrated salt and concentrated solution, and cooling the concentrated solution to 10 ℃ while the concentrated solution is hot to carry out solid-liquid separation to obtain cooled salt and third purified solution. Drying the concentrated salt and the cooled salt to obtain anhydrous sodium sulphate meeting the standard. The loss rate of lithium in this step was 0.50%.
And adding a sodium carbonate solution into the third purified liquid to adjust the pH value to 10.0, and carrying out solid-liquid separation to obtain the final purified liquid. The Ca removal rate was 98.4%.
Heating the final purified liquid to boiling, adding 330g/L sodium carbonate solution to react for 60min, performing solid-liquid separation to obtain precipitated lithium carbonate, washing by adopting saturated lithium carbonate solution according to the wet-weight mass ratio of the precipitate of 1.5:1, and drying to obtain a lithium carbonate product (Li) meeting the national standard GB/T11075-20132CO399.88%), the precipitation rate of lithium reached 85.43%.
Example 3
Li-containing lithium ore of certain sedimentary type in Guizhou2O 0.58％，Al2O3 58.07％，SiO2 21.59％。
A comprehensive recycling method of a deposition type lithium resource comprises the following steps:
the lithium-containing bauxite is crushed and ground into fine powder to obtain fine-grained mineral, and the content of the lithium-containing bauxite of-200 meshes in the fine-grained mineral is 80%.
Adding sulfuric acid into fine minerals to adjust the pH value of ore pulp to 6, adopting a flotation process of primary roughing, primary concentrating and twice scavenging to perform separation, wherein the dosage of a medicament for the primary roughing is 100g/t of potassium chloride and 75g/t of sodium hexametaphosphate, adding 90g/t of ether amine, and performing the primary concentratingThe dosage of the medicament is 25g/t of sodium hexametaphosphate, 40g/t of ether amine in the medicament dosage for one scavenging and 20g/t of ether amine in the medicament dosage for the second scavenging to obtain the Al2O3Grade 71.68% Al2O3Bauxite concentrate product with recovery rate of 70.10% and Al-Si ratio of 8.33 and Li2O grade 1.25%, Li2And the recovery rate of O is 93.13 percent of the lithium-rich product.
Taking 1500g of a lithium-rich product, and mixing concentrated sulfuric acid with the mass concentration of 50% and the lithium-rich product according to the volume mass ratio of 1.5:1, curing and reacting for 60min at the temperature of 160 ℃ to obtain the lithium-containing clinker. Stirring and leaching the lithium-containing clinker by using 1.0L of water, wherein the leaching temperature is 25 ℃, the leaching time is 60min, then carrying out solid-liquid separation to obtain a lithium-containing leaching solution, and the leaching rate of lithium reaches 92.19%.
Adding sufficient hydrogen peroxide into the lithium-containing leachate, adding a sodium hydroxide solution after complete reaction to adjust the pH to 3.5, carrying out solid-liquid separation and retaining a first purified solution.
And adding a sodium hydroxide solution into the first purified liquid to adjust the pH value to 6.9, carrying out solid-liquid separation after complete reaction, and reserving the second purified liquid. In this case, the Fe removal rate was 99.99%, the Al removal rate was 99.97%, and the loss rate of lithium was as small as 1.92%.
And (3) carrying out solid-liquid separation on the second filtrate in a boiling state when the second filtrate is evaporated and concentrated to the original volume of 1/9 to obtain concentrated salt and concentrated solution, and cooling the concentrated solution to 15 ℃ while the concentrated solution is hot to carry out solid-liquid separation to obtain cooled salt and third purified solution. Drying the concentrated salt and the cooled salt to obtain anhydrous sodium sulphate meeting the standard. The loss rate of lithium in this step was 0.47%.
And adding a sodium carbonate solution into the third purified liquid to adjust the pH value to 9.5, and then carrying out solid-liquid separation to obtain calcium slag and a final purified liquid. The Ca removal rate was 97.8% at this time
Heating the final purified liquid to boiling, adding 320g/L sodium carbonate solution to react for 45min, performing solid-liquid separation to obtain precipitated lithium carbonate, washing with deionized water at 95 ℃ according to the wet-weight mass ratio of the precipitate of 1.2:1, and drying to obtain a lithium carbonate product (Li) meeting the national standard GB/T11075-20132CO399.67%) and the precipitation rate of lithium reached 84.83%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A comprehensive recycling method of deposition type lithium resources is characterized in that: the method comprises the following steps:
s1: crushing and grinding the sedimentary lithium ore to 70-80% of the granularity smaller than 0.074mm to obtain fine-grained minerals;
s2: performing flotation on the fine-grained minerals to obtain flotation concentrate and flotation tailings, wherein the flotation concentrate is a lithium-rich product, and the flotation tailings are bauxite concentrate products;
s3: carrying out sulfuric acid curing and water leaching on the lithium-rich product to convert lithium from a solid phase to a liquid phase to obtain lithium-containing leachate;
s4: purifying the leachate to remove impurities, and removing impurities such as iron, aluminum, sodium and calcium to obtain a final purified solution;
s5: and adding sodium carbonate into the final purified liquid obtained in the step S4 for reaction, precipitating a precipitate after the reaction is completed, and washing and drying the precipitate to obtain lithium carbonate.
2. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 1, wherein: in step S1, Li in deposit-type lithium ore2The grade of O is 0.1-0.6%, Al2O3Grade of (2)>50% of Al/Si ratio>2.6。
3. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 1, wherein: in step S3, the raw material for sulfuric acid curing is concentrated sulfuric acid with mass concentration of 50% -80%, the curing temperature is 120-175 ℃, the curing liquid-solid ratio is 0.5-2:1, and the curing time is 20-100 min.
4. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 1, characterized in that: in step S3, the water immersion temperature is normal temperature, the solid ratio of the water immersion liquid is 0.5-2:1, and the water immersion time is 5-30 min.
5. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 1, wherein: in step S2, the flotation method includes: adjusting the pH value of the ore pulp to 4-6 by sulfuric acid or hydrochloric acid in the fine-grained minerals; and then adding 20-100 g/t of an activating agent, 40-100 g/t of an inhibitor and 50-150 g/t of a collecting agent, wherein the activating agent is sodium chloride or potassium chloride, the inhibitor is one or two of sodium hexametaphosphate and polyacrylamide, and the collecting agent is one or more of fatty amine, ether amine and quaternary ammonium salt.
6. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 1, wherein: in step S4, the method for removing iron by purification includes: adding oxidant into the leaching solution to lead Fe in the leaching solution to be2+All converted to Fe3+Then adding a pH regulator to adjust the pH of the leachate to 3.5-4.0, precipitating iron, and carrying out solid-liquid separation to obtain iron slag and primary purification liquid; the oxidant is one or two of hydrogen peroxide and sodium peroxide, and the pH regulator is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate.
7. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 6, wherein: in step S4, the method for removing aluminum by purification comprises: adding a pH regulator into the primary purification liquid to regulate the pH of the leachate to 6.0-7.0, precipitating aluminum, and carrying out solid-liquid separation to obtain aluminum slag and secondary purification liquid; the pH regulator is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate solution.
8. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 7, wherein: in step S4, the method for purifying and removing sodium includes: concentrating the secondary purified liquid until the volume ratio of the secondary purified liquid to the original purified liquid is 1 (8-10), then carrying out solid-liquid separation to obtain concentrated salt and concentrated liquid, cooling the concentrated liquid to 10-20 ℃, and carrying out solid-liquid separation to obtain cooled salt and tertiary purified liquid.
9. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 8, wherein: in step S4, the method for purifying and removing calcium comprises: and adding sodium carbonate into the third purified liquid, adjusting the pH value to 9.5-10.5, precipitating calcium ions in the third purified liquid in the form of calcium carbonate, and performing solid-liquid separation to obtain calcium slag and final purified liquid.
10. The comprehensive recycling method of sedimentary lithium resources as claimed in claim 1, characterized in that: in the step S5, a 330g/L sodium carbonate solution with the mass concentration of 300-100 ℃ is added into the final purification solution, the reaction temperature is 90-100 ℃, the reaction time is 20-60min, the bottom is washed by using a washing solution, the washing solution is 80-95 ℃ deionized water or a saturated solution of lithium carbonate, and the ratio of the usage amount of the washing solution to the wet weight of the lithium carbonate is 1-1.5: 1.
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