CN114751434B - Comprehensive recycling method of deposition type lithium resources - Google Patents
Comprehensive recycling method of deposition type lithium resources Download PDFInfo
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- CN114751434B CN114751434B CN202210470990.XA CN202210470990A CN114751434B CN 114751434 B CN114751434 B CN 114751434B CN 202210470990 A CN202210470990 A CN 202210470990A CN 114751434 B CN114751434 B CN 114751434B
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- solution
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 230000008021 deposition Effects 0.000 title claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 47
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 44
- 239000000047 product Substances 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000005188 flotation Methods 0.000 claims abstract description 27
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 23
- 239000011707 mineral Substances 0.000 claims abstract description 23
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 18
- 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 16
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 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 103
- 239000000243 solution Substances 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 235000010755 mineral Nutrition 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 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
- 238000001816 cooling Methods 0.000 claims description 12
- 229910052742 iron 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
- 239000002893 slag Substances 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 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
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000001376 precipitating effect Effects 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
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 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
- 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
- 229910018125 Al-Si Inorganic materials 0.000 claims description 3
- 229910018520 Al—Si Inorganic materials 0.000 claims description 3
- 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 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000012047 saturated solution Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 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
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000013049 sediment 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a comprehensive recycling method of a deposition type lithium resource, which comprises the following steps: grinding the deposited lithium ore to obtain fine-grained mineral; carrying out 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 transfer lithium from a solid phase to a liquid phase to obtain a lithium-containing leaching solution; purifying the leaching solution to remove impurities to obtain a final purified solution; and adding sodium carbonate into the final purified solution for reaction, separating out precipitate after the reaction is completed, washing and drying the precipitate to obtain lithium carbonate. The method provided by the invention is used for treating the deposited lithium ore, obtaining a bauxite concentrate product and a high-purity lithium carbonate product, realizing comprehensive recycling and utilization of deposited lithium resources, saving energy and reducing consumption, enabling the high-purity lithium carbonate product to reach a battery level, meeting the requirements of the battery quality standard of new energy industry, and being applicable to manufacturing 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 deposition type lithium resources.
Background
Lithium is the lightest metal in nature and has wide application in the traditional fields such as glass, ceramics, metallurgical industry, medicine, organic synthesis and the like. At present, china is fully promoting the transformation and upgrading of the traditional industry. Lithium penetrates ten fields of new generation information technology industry, high-grade numerical control machine tools and robots, energy-saving and new energy automobiles, electric power equipment, new materials, biological medicines, high-performance medical appliances and the like, and is a key mineral product essential for development of the future strategic emerging industry of China, and is also called white petroleum. China is the first big lithium consuming country, global lithium consumption in 2018 is about 4.76 ten thousand tons, chinese consumption is close to 50% of the world, but the external dependence of Chinese lithium resources is more than 80%, so searching for new lithium resources is urgent.
Currently, there are mainly 3 types of lithium deposits found in nature: brine type of salt lake, granite-peganite-basic long granite type and sediment type. Compared with the main world lithium resource country, china is not dominant in the resource amount of the first 2 types of ore deposits, and the deposited lithium ore is a potential lithium resource library. The lithium content in Chinese bauxite (rock) stands in front of various deposition type lithium ores, and the ascertained reserve of Chinese bauxite exceeds 50 hundred million tons, the basic reserve exceeds 10 hundred million tons, and the reserve of associated lithium resources is quite considerable. However, china has not independently developed and utilized the sedimentary lithium ores.
Document CN110042262a discloses a method for selectively leaching low-grade deposit-type lithium ore, which comprises roasting at 500-700 ℃ to obtain cooked ore, leaching the cooked ore with inorganic acid at 20-60 ℃ to obtain lithium-rich solution. The method has the advantages of higher roasting reaction temperature and high energy consumption, and meanwhile, part of silicon element is leached into solution in the method, so that the subsequent impurity removal difficulty is increased, only the leaching condition of lithium solution is examined, and the method has no relation to the subsequent impurity removal and extraction.
Disclosure of Invention
The invention provides a comprehensive recycling method of a deposited lithium resource, which can obtain qualified bauxite concentrate products and high-purity lithium carbonate products, realizes the comprehensive recycling and utilization of the deposited lithium resource, 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 requirement of the quality standard of the new energy industry battery, and can be applied to manufacturing the lithium battery in the new energy automobile.
The technical scheme of the invention is realized as follows: a comprehensive recycling method of a deposition type lithium resource comprises the following steps:
s1: grinding the deposited lithium ore until the granularity is smaller than 0.074mm and the proportion is 70-80%, thus obtaining fine-grained minerals;
s2: carrying out 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 transfer lithium from a solid phase to a liquid phase to obtain a lithium-containing leaching solution;
s4: purifying the leaching solution to remove impurities such as iron, aluminum, sodium and calcium to obtain a final purified solution;
s5: and (3) adding sodium carbonate into the final purifying liquid in the step (S4), reacting at 90-100 ℃, separating out precipitate after the reaction is complete, washing and drying the precipitate to obtain lithium carbonate.
Further, in step S1, li in the deposit type lithium ore 2 The grade of O is 0.1 to 0.6 percent, al 2 O 3 Grade of (2)>50% Al-Si ratio>2.6。
In the step S3, the raw material for curing the sulfuric acid is concentrated sulfuric acid with the 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 the step S3, the water immersion temperature is normal temperature, the water immersion solid ratio is 0.5-2:1, and the water immersion time is 5-30 min.
Further, in step S2, the flotation method is as follows: adjusting the pH value of the ore pulp to 4-6 by sulfuric acid or hydrochloric acid in the fine-grained minerals; then 20-100 g/t of activating agent, 40-100 g/t of inhibitor and 50-150 g/t of collecting agent are added, 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, etheramine and quaternary ammonium salt.
Further, in step S4, the method for purifying and removing iron is as follows: adding an oxidant into the leaching solution to enable Fe in the leaching solution to be 2+ All are converted into Fe 3+ Then adding a pH regulator to adjust the pH of the leaching solution to 3.5-4.0, precipitating iron, and carrying out solid-liquid separation to obtain iron slag and primary purifying 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 purifying and removing aluminum includes: adding a pH regulator into the primary purifying liquid to regulate the pH of the leaching liquid to 6.0-7.0, precipitating aluminum, and carrying out solid-liquid separation to obtain aluminum slag and secondary purifying 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 is as follows: concentrating the secondary purifying liquid to the volume ratio of 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 cooling salt and tertiary purifying liquid;
further, in step S4, the method for purifying and removing calcium is as follows: adding sodium carbonate into the tertiary purifying liquid, regulating the pH value to 9.5-10.5, separating out calcium ions in the tertiary purifying liquid in the form of calcium carbonate, and carrying out solid-liquid separation to obtain calcium slag and final purifying liquid.
Further, in the step S5, a sodium carbonate solution with the mass concentration of 300-330g/L is added into the final purifying solution, the reaction temperature is 90-100 ℃, the reaction time is 20-60min, the bottom is washed by adopting a washing solution, the washing solution is deionized water or saturated solution of lithium carbonate with the temperature of 80-95 ℃, and the ratio of the consumption of the washing solution to the wet weight of the lithium carbonate is 1-1.5:1.
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 deposited lithium resource is realized, the leaching rate of lithium reaches above 92 percent by adopting the cooperation of grinding-floatation and sulfuric acid curing water leaching, high-temperature roasting is not needed, energy is saved, consumption is reduced, the subsequent purification and impurity removal of the lithium-containing leaching solution are carried out, the Fe removal rate is above 99.9 percent, the Al removal rate is above 99.9 percent, the Ca removal rate is above 99 percent, the lithium loss rate is small in the whole impurity removal process, the precipitation rate of lithium reaches above 84 percent, the purity of the lithium carbonate product reaches above 99.5 percent, the battery grade is reached, the requirement of the battery quality standard of the new energy industry is met, and the method can be applied to the manufacture of lithium batteries in new energy automobiles. The invention not only recovers lithium resources, but also recovers aluminum resources. At present, no independent development and utilization of the deposition type lithium ore exist at home, the invention realizes the technical increase and storage of lithium, and can relieve the external dependence of lithium resources.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for comprehensively recycling deposited lithium resources;
fig. 2 is a process flow of flotation in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, a comprehensive recycling method of a deposition type lithium resource includes the following steps:
s1: grinding the deposited lithium ore until the granularity is smaller than 0.074mm and the proportion is 70-80%, thus obtaining fine-grained minerals;
s2: carrying out 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 transfer lithium from a solid phase to a liquid phase to obtain a lithium-containing leaching solution;
s4: purifying the leaching solution to remove impurities such as iron, aluminum, sodium and calcium to obtain a final purified solution;
s5: and (3) adding sodium carbonate into the final purifying liquid in the step (S4), reacting at 90-100 ℃, separating out precipitate after the reaction is complete, washing and drying the precipitate to obtain lithium carbonate.
In step S1, li in the deposit type lithium ore 2 The grade of O is 0.1 to 0.6 percent, al 2 O 3 Grade of (2)>50% Al-Si ratio>2.6。
In the step S3, the raw material for curing the sulfuric acid is concentrated sulfuric acid with the 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 the step S3, the water immersion temperature is normal temperature, the water immersion solid ratio is 0.5-2:1, and the water immersion time is 5-30 min.
In the step S2, the flotation method comprises the following steps: adjusting the pH value of the ore pulp to 4-6 by sulfuric acid or hydrochloric acid in the fine-grained minerals; then 20-100 g/t of activating agent, 40-100 g/t of inhibitor and 50-150 g/t of collecting agent are added, 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, etheramine and quaternary ammonium salt.
In the step S4, the method for purifying and removing iron comprises the following steps: adding an oxidant into the leaching solution to enable Fe in the leaching solution to be 2+ All are converted into Fe 3+ Then adding a pH regulator to adjust the pH of the leaching solution to 3.5-4.0, precipitating iron, and carrying out solid-liquid separation to obtain iron slag and primary purifying 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 the step S4, the method for purifying and removing aluminum comprises the following steps: adding a pH regulator into the primary purifying liquid to regulate the pH of the leaching liquid to 6.0-7.0, precipitating aluminum, and carrying out solid-liquid separation to obtain aluminum slag and secondary purifying liquid; the pH regulator is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate solution.
In the step S4, the method for purifying and removing sodium comprises the following steps: concentrating the secondary purifying liquid to the volume ratio of 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 cooling salt and tertiary purifying liquid.
In the step S4, the method for purifying and removing calcium comprises the following steps: adding sodium carbonate into the tertiary purifying liquid, regulating the pH value to 9.5-10.5, separating out calcium ions in the tertiary purifying liquid in the form of calcium carbonate, and carrying out solid-liquid separation to obtain calcium slag and final purifying liquid.
In the step S5, adding 300-330g/L sodium carbonate solution into the final purifying liquid, wherein the reaction temperature is 90-100 ℃, the reaction time is 20-60min, washing the bottom by adopting washing liquid, the washing liquid is 80-95 ℃ deionized water or saturated solution of lithium carbonate, and the ratio of the consumption of the washing liquid to the wet weight of the lithium carbonate is 1-1.5:1.
Specific examples are as follows:
example 1
Certain deposit type lithium ore in Guizhou, li 2 O 0.13％，Al 2 O 3 58.62％，SiO 2 20.86% of the total amount of the main minerals are diasporite, kaolinite and illite, and lithium is mainly contained in minerals such as kaolinite and illite.
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 into fine powder, and fine-grained mineral is obtained, wherein the content of the-200 meshes of lithium-containing bauxite is 70 percent.
Adding sulfuric acid into fine-grained minerals to adjust the pH value of ore pulp to be 4, sorting by adopting a flotation process of primary roughing, primary concentration and secondary scavenging, wherein the dosage of the primary roughing agent is 20g/t of potassium chloride, 40g/t of polyacrylamide, 50g/t of dodecylamine is added, the dosage of the primary concentration agent is 20g/t of polyacrylamide, the dosage of the primary scavenging agent is 25g/t of dodecylamine, and the dosage of the secondary scavenging agent is 20g/t of dodecylamine, thereby obtaining Al 2 O 3 Grade is 64.23%, al 2 O 3 Bauxite concentrate product with recovery rate of 75.47% and aluminium-silicon ratio of 6.72 and Li 2 The grade of O is 0.36 percent, li 2 And the recovery rate of O is 86.18 percent of the lithium-rich product.
1500g of lithium-rich product is taken, and concentrated sulfuric acid with the mass concentration of 80% and the lithium-rich product are mixed according to the volume-mass ratio of 1: and (3) uniformly mixing the materials according to the proportion, and curing the materials at 175 ℃ for 100 minutes to obtain the lithium-containing clinker. The method comprises the steps of stirring and leaching the lithium-containing clinker by 3.0L of water, wherein the leaching temperature is 25 ℃, and the leaching time is 10min, and then carrying out solid-liquid separation to obtain the lithium-containing leaching solution.
And adding a sufficient amount of hydrogen peroxide into the leaching solution containing lithium, adding sodium hydroxide solution to adjust the pH to 4.0 after complete reaction, performing solid-liquid separation, and retaining the first purifying liquid.
And adding sodium hydroxide solution into the first purified liquid to adjust the pH value to 6.5, and carrying out solid-liquid separation and retaining the second purified liquid after complete reaction. At this time, the Fe removal rate was 99.95%, the Al removal rate was 99.94%, and the lithium loss rate was small, which was only 1.94%.
And (3) evaporating and concentrating the second purified liquid to 1/8 of the original volume in a boiling state, performing solid-liquid separation to obtain concentrated salt and concentrated liquid, and cooling the concentrated liquid to 10 ℃ while the concentrated liquid is hot, and performing solid-liquid separation to obtain cooled salt and third purified liquid. And drying the concentrated salt and the cooling salt to obtain anhydrous sodium sulfate meeting the standard. The loss rate of lithium in this step was 0.36%.
And adding sodium carbonate solution into the third purifying liquid to adjust the pH value to 10.5, and then carrying out solid-liquid separation to obtain the final purifying liquid, wherein the Ca removal rate is 99.2%.
Heating the final purifying liquid to boiling, adding 300g/L to obtain sodium carbonate solution, reacting for 30min, performing solid-liquid separation to obtain precipitated lithium carbonate, washing with 95 ℃ deionized water according to a wet weight ratio of 1:1, and drying to obtain a lithium carbonate product (Li 2 CO 3 99.56 percent) and the precipitation rate of lithium reaches 84.52 percent.
Example 2
Certain sedimentary lithium ore in the West of China contains Li 2 O 0.27％，Al 2 O 3 52.87％，SiO 2 16.87% of the total amount of lithium and the main minerals are diasporite, kaolinite, illite, and lithium is mainly contained in minerals such as kaolinite and illite.
The comprehensive recycling method of the deposition type lithium resource comprises the following steps:
the lithium-containing bauxite is crushed into fine powder, and fine-grained mineral is obtained, wherein the content of the-200 meshes of lithium-containing bauxite is 75%. Adding sulfuric acid into fine-grained minerals to adjust the pH value of ore pulp to be 5, sorting by adopting a flotation process of primary roughing, primary concentration and primary scavenging, wherein the dosage of the primary roughing agent is 60g/t of sodium chloride, 40g/t of sodium hexametaphosphate, 75g/t of dodecyl amine is added, the dosage of the primary concentration agent is 20g/t of sodium hexametaphosphate, and the dosage of the primary scavenging agent is 25g/t of dodecyl amine, thereby obtaining Al 2 O 3 Grade is 65.32%, al 2 O 3 Bauxite concentrate product with recovery rate of 76.39% and aluminium-silicon ratio of 8.7 and Li 2 The grade of O is 0.65 percent, li 2 And the recovery rate of O is 91.89 percent of the lithium-rich product.
1500g of lithium-rich product is taken, and the mass concentration of the concentrated sulfuric acid with the mass concentration of 75 percent is calculated with the lithium-rich product according to the volume-mass ratio of 2: and (3) uniformly mixing the materials according to the proportion, and curing the materials at the temperature of 150 ℃ for 90 minutes to obtain the lithium-containing clinker. And leaching the lithium-containing clinker by adopting 2.0L of water under stirring, wherein the leaching temperature is 25 ℃, and after the leaching time is 30min, solid-liquid separation is carried out to obtain a leaching solution containing lithium, and the leaching rate of the lithium reaches 93.58%.
Adding enough sodium peroxide into the leaching solution containing lithium, adding sodium hydroxide solution to adjust the pH value to 3.9 after complete reaction, performing solid-liquid separation and retaining the first purifying liquid.
And adding sodium hydroxide solution into the first purified liquid to adjust the pH value to 6.8, and carrying out solid-liquid separation and retaining the second purified liquid after complete reaction. At this time, the Fe removal rate was 99.98%, the Al removal rate was 99.95%, and the lithium loss rate was small, which was only 1.88%.
And (3) evaporating and concentrating the second filtrate to 1/10 of the original volume in a boiling state, performing solid-liquid separation to obtain concentrated salt and concentrated solution, and cooling the concentrated solution to 10 ℃ while the concentrated solution is hot, performing solid-liquid separation to obtain cooled salt and third purified solution. And drying the concentrated salt and the cooling salt to obtain anhydrous sodium sulfate meeting the standard. The loss rate of lithium in this step was 0.50%.
And adding sodium carbonate solution into the third purifying liquid to adjust the pH value to 10.0, and then carrying out solid-liquid separation to obtain the final purifying liquid. At this time, the Ca removal rate was 98.4%.
Heating the final purifying liquid to boiling, adding 330g/L to obtain sodium carbonate solution, reacting for 60min, performing solid-liquid separation to obtain precipitated lithium carbonate, washing with saturated lithium carbonate solution according to a wet weight ratio of 1.5:1, and drying to obtain a lithium carbonate product (Li 2 CO 3 99.88%), the precipitation rate of lithium reaches 85.43%.
Example 3
Certain deposit type lithium ore in Guizhou, li 2 O 0.58％，Al 2 O 3 58.07％，SiO 2 21.59％。
The comprehensive recycling method of the deposition type lithium resource comprises the following steps:
the lithium-containing bauxite is crushed into fine powder, and fine-grained mineral is obtained, wherein the content of the-200 meshes of lithium-containing bauxite in the fine-grained mineral is 80 percent.
Adding sulfuric acid into fine-grained minerals to adjust the pH value of ore pulp to 6, and adopting flotation processes of primary roughing, primary concentration and secondary scavenging to sort, wherein the dosage of the primary roughing agent is 100g/t of potassium chloride, 75g/t of sodium hexametaphosphate, 90g/t of etheramine is added, the dosage of the primary concentration agent is 25g/t of sodium hexametaphosphate, the dosage of the primary scavenging agent is 40g/t of etheramine, the dosage of the secondary scavenging agent is 20g/t of etheramine, and Al is obtained 2 O 3 Grade of 71.68%, al 2 O 3 Bauxite concentrate product with recovery rate of 70.10% and aluminium-silicon ratio of 8.33 and Li 2 The grade of O is 1.25 percent, li 2 The recovery rate of O is 93.13 percent of the lithium-rich product.
1500g of lithium-rich product is taken, and the mass concentration of 50% is that of concentrated sulfuric acid and the lithium-rich product according to the volume-mass ratio of 1.5: and (3) uniformly mixing the materials according to the proportion, and curing the materials at 160 ℃ for 60 minutes to obtain the lithium-containing clinker. And (3) stirring and leaching the lithium-containing clinker by adopting 1.0L of water, wherein the leaching temperature is 25 ℃, and after the leaching time is 60min, solid-liquid separation is carried out to obtain a lithium-containing leaching solution, and the leaching rate of lithium reaches 92.19%.
And adding a sufficient amount of hydrogen peroxide into the leaching solution containing lithium, adding sodium hydroxide solution to adjust the pH to 3.5 after complete reaction, performing solid-liquid separation, and retaining the first purifying liquid.
And adding sodium hydroxide solution into the first purified liquid to adjust the pH value to 6.9, and carrying out solid-liquid separation and retaining the second purified liquid after complete reaction. At this time, the Fe removal rate was 99.99%, the Al removal rate was 99.97%, and the lithium loss rate was small, which was only 1.92%.
And (3) evaporating and concentrating the second filtrate to 1/9 of the original volume in a boiling state, performing solid-liquid separation to obtain concentrated salt and concentrated solution, and cooling the concentrated solution to 15 ℃ while the concentrated solution is hot, performing solid-liquid separation to obtain cooled salt and third purified solution. And drying the concentrated salt and the cooling salt to obtain anhydrous sodium sulfate meeting the standard. The loss rate of lithium in this step was 0.47%.
And adding sodium carbonate solution into the third purifying liquid to adjust the pH value to 9.5, and then carrying out solid-liquid separation to obtain calcium slag and final purifying liquid. At this time, the Ca removal rate was 97.8%
Heating the final purifying liquid to boiling, adding 320g/L to obtain sodium carbonate solution, reacting for 45min, performing solid-liquid separation to obtain precipitated lithium carbonate, washing with 95 ℃ deionized water according to a wet weight ratio of 1.2:1, and drying to obtain a lithium carbonate product (Li) meeting national standard GB/T11075-2013 2 CO 3 99.67 percent) and the precipitation rate of lithium reaches 84.83 percent.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (3)
1. A comprehensive recycling method of a deposition type lithium resource is characterized in that: the method comprises the following steps:
s1: grinding the deposited lithium ore until the granularity is smaller than 0.074mm and the proportion is 70-80%, thus obtaining fine-grained minerals;
s2: carrying out 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 transfer lithium from a solid phase to a liquid phase to obtain a lithium-containing leaching solution;
s4: purifying the leaching solution to remove impurities such as iron, aluminum, sodium and calcium to obtain a final purified solution;
s5: adding sodium carbonate into the final purifying liquid in the step S4 for reaction, separating out precipitate after the reaction is completed, washing and drying the precipitate to obtain lithium carbonate;
in step S1, li in the deposit type lithium ore 2 The grade of O is 0.1 to 0.6 percent, al 2 O 3 Grade of (2)>50% Al-Si ratio>2.6；
In the step S2, the flotation method comprises the following steps: adjusting the pH value of the ore pulp to 4-6 by sulfuric acid or hydrochloric acid in the fine-grained minerals; then 20-100 g/t of activating agent, 40-100 g/t of inhibitor and 50-150 g/t of collecting agent are added, 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, etheramine and quaternary ammonium salt;
in the step S3, the raw material for curing the sulfuric acid is concentrated sulfuric acid with the 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 the step S3, the water immersion temperature is normal temperature, the water immersion solid ratio is 0.5-2:1, and the water immersion time is 5-30 min;
in the step S4, the method for purifying and removing iron comprises the following steps: adding an oxidant into the leaching solution to enable Fe in the leaching solution to be 2+ All are converted into Fe 3+ Then adding a pH regulator to adjust the pH of the leaching solution to 3.5-4.0, precipitating iron, and carrying out solid-liquid separation to obtain iron slag and primary purifying 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 the step S4, the method for purifying and removing aluminum comprises the following steps: adding a pH regulator into the primary purifying liquid to regulate the pH of the leaching liquid to 6.0-7.0, precipitating aluminum, and carrying out solid-liquid separation to obtain aluminum slag and secondary purifying liquid; the pH regulator is one or two of sodium hydroxide, sodium carbonate and sodium bicarbonate solution;
in the step S4, the method for purifying and removing sodium comprises the following steps: concentrating the secondary purifying liquid to the volume ratio of 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 cooling salt and tertiary purifying liquid.
2. The method for comprehensively recycling the deposited lithium resources according to claim 1, wherein the method comprises the following steps: in the step S4, the method for purifying and removing calcium comprises the following steps: adding sodium carbonate into the tertiary purifying liquid, regulating the pH value to 9.5-10.5, separating out calcium ions in the tertiary purifying liquid in the form of calcium carbonate, and carrying out solid-liquid separation to obtain calcium slag and final purifying liquid.
3. The method for comprehensively recycling the deposited lithium resources according to claim 1, wherein the method comprises the following steps: in the step S5, adding 300-330g/L sodium carbonate solution into the final purifying liquid, wherein the reaction temperature is 90-100 ℃, the reaction time is 20-60min, washing the bottom by adopting washing liquid, the washing liquid is 80-95 ℃ deionized water or saturated solution of lithium carbonate, and the ratio of the consumption of the washing liquid to the wet weight of the lithium carbonate is 1-1.5:1.
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| TR2022013883A2 (en) * | 2022-09-06 | 2022-09-21 | Eti Alueminyum Anonim Sirket | METHOD OF PRODUCTION FROM BOXIDE ORE OF LITHIUM CARBONATE USED IN THE CATHODED MATERIAL OF LI-ION BATTERIES |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720339A (en) * | 1985-03-15 | 1988-01-19 | American Cyanamid Company | Flotation beneficiation process for non-sulfide minerals |
| EP3156540A1 (en) * | 2015-10-12 | 2017-04-19 | Omya International AG | Process for the deinking of coated paper or paperboard |
| CN107265486A (en) * | 2017-07-28 | 2017-10-20 | 贵州大学 | The method that lithium carbonate is prepared using pelite containing lithium |
| WO2018192122A1 (en) * | 2017-04-18 | 2018-10-25 | 中科过程（北京）科技有限公司 | Method for mixed acid leaching and recovery of positive electrode materials of waste lithium ion batteries |
| CN109225648A (en) * | 2018-10-23 | 2019-01-18 | 中国地质科学院郑州矿产综合利用研究所 | Pegmatite type spodumene flotation collecting agent and preparation method and application thereof |
| CN113825848A (en) * | 2019-03-29 | 2021-12-21 | 锂业美洲公司 | Method for extracting lithium from sedimentary clay |
| RU2768719C1 (en) * | 2021-09-22 | 2022-03-24 | Общество с ограниченной ответственностью "Русский Кобальт" (ООО "РК") | Method of recycling spent lithium-ion batteries |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2882998B1 (en) * | 2005-03-08 | 2007-06-08 | Solvay | PROCESS FOR OBTAINING SODIUM CARBONATE CRYSTALS |
| EP3204528B1 (en) * | 2014-10-10 | 2020-07-01 | Li-Technology Pty Ltd. | Recovery process |
| PT3417082T (en) * | 2016-02-18 | 2022-11-08 | Li Tech Pty Ltd | Lithium recovery from phosphate minerals |
| CN109336142B (en) * | 2018-12-26 | 2020-06-05 | 北京化工大学 | Method for extracting lithium from salt lake brine and preparing aluminum hydroxide simultaneously |
-
2022
- 2022-04-28 CN CN202210470990.XA patent/CN114751434B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720339A (en) * | 1985-03-15 | 1988-01-19 | American Cyanamid Company | Flotation beneficiation process for non-sulfide minerals |
| EP3156540A1 (en) * | 2015-10-12 | 2017-04-19 | Omya International AG | Process for the deinking of coated paper or paperboard |
| WO2018192122A1 (en) * | 2017-04-18 | 2018-10-25 | 中科过程（北京）科技有限公司 | Method for mixed acid leaching and recovery of positive electrode materials of waste lithium ion batteries |
| CN107265486A (en) * | 2017-07-28 | 2017-10-20 | 贵州大学 | The method that lithium carbonate is prepared using pelite containing lithium |
| CN109225648A (en) * | 2018-10-23 | 2019-01-18 | 中国地质科学院郑州矿产综合利用研究所 | Pegmatite type spodumene flotation collecting agent and preparation method and application thereof |
| CN113825848A (en) * | 2019-03-29 | 2021-12-21 | 锂业美洲公司 | Method for extracting lithium from sedimentary clay |
| RU2768719C1 (en) * | 2021-09-22 | 2022-03-24 | Общество с ограниченной ответственностью "Русский Кобальт" (ООО "РК") | Method of recycling spent lithium-ion batteries |
Non-Patent Citations (1)
| Title |
|---|
| 贵州某铝土矿选矿试验;陈丽荣;杨国彬;黄苑龄;张周位;;现代矿业(04);全文 * |
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