CN112678851B - Preparation method of low-cost battery-grade lithium carbonate - Google Patents
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Abstract
The invention discloses a preparation method of low-cost battery-grade lithium carbonate, which takes lithium extraction from spodumene or lepidolite ore, lithium extraction from salt lake brine or underground brine and lithium slag generated in the production process of butyl lithium as raw materials, and generates lithium carbonate, carbon content, calcination and other processes through the processes of crushing, screening, uniformly mixing with carbonate, mechanical grinding, deposition and the like, and has the characteristics of stable process, low cost and the like.
Description
Technical Field
The invention relates to the technical field of battery-grade lithium carbonate preparation, in particular to a preparation method of low-cost battery-grade lithium carbonate.
Background
Lithium resources exist mainly in the form of salt lakes and spodumene ores. Spodumene slag is one of industrial solid wastes, is industrial solid waste slag generated after lithium carbonate is extracted from spodumene ore industrially, has very large yield of spodumene slag at home and abroad, and a small part of unreacted metal lithium exists in residual liquid in the production process of butyl lithium, is hydrolyzed to become lithium hydroxide, and is discharged together with lithium chloride as lithium slag. The slag after the lithium extraction from the salt lake brine contains lithium chloride. If not used, the method not only occupies a large space for stacking, but also is inconvenient to manage, and residue water containing a certain amount of acid or alkali is easy to lose after being washed by rainwater, thus harming the surrounding farmlands and causing pollution. There is currently a lack of treatment routes for these lithium slags.
Lithium carbonate (Li) 2 CO 3 ) It can be used as fluxing agent and additive in the course of glass production and ceramic production, also can be used as intermediate raw material for producing other lithium salts, for example, for producing surface elastic wave element material lithium tantalate and lithium niobate monocrystal, etc. In recent years, with the exposure of high-quality lithium salt in high and new technical fields such as new energy and new materials, particularly in the field of electric automobiles, lithium carbonate shows an attractive application prospect.
At present, the technology for producing lithium carbonate by taking spodumene as a raw material comprises a limestone roasting method, a soda ash pressure cooking method, a transformation roasting-sulfuric acid method and the like, and the production processes have the defects of low product purity, narrow raw material source range and high cost.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of low-cost battery-grade lithium carbonate, which replaces more expensive and scarce lepidolite, solves the problem of high cost when LiOH is directly used as a raw material, reduces the production cost of lithium carbonate, and has the advantages of stable process and simple preparation method.
In order to achieve the purpose, the invention adopts the specific scheme that:
a preparation method of low-cost battery-grade lithium carbonate is characterized by comprising the following steps:
(1) Coarse crushing, ball milling and screening the lithium slag to ensure that the lithium slag with the granularity lower than 100 meshes accounts for more than 80 percent of the total lithium slag;
(2) Uniformly mixing the sieved lithium slag and carbonate according to the mass ratio of 5:1, and then fully mechanically grinding;
(3) And (3) adding deionized water into the powder obtained after mechanical grinding in the step (2) to obtain a powder with a solid-to-liquid ratio of 1: reacting the suspension obtained in the step (1-2) at 90-95 ℃ for 1h, and filtering by using a suction filter to obtain filter residues;
(4) And (4) adding deionized water into the filter residue obtained in the step (3) at room temperature to obtain a mixture with a solid-to-liquid ratio of 1: (2 to 3) and introducing an excessive amount of CO into the suspension 2 ；
(5) Filtering the suspension obtained in the step (4), removing filter residues, heating the filtrate to 70-75 ℃, and then vacuumizing, wherein the vacuum degree is maintained at 0.2-0.25 atm for 1 hour;
(6) And (5) carrying out suction filtration on the solid-liquid mixture obtained in the step (5) to obtain Li 2 CO 3 Washing the crude product with deionized water to remove Li 2 CO 3 Soluble impurity ions in the crude product and drying for 2h at 100-105 ℃ to obtain Li with the purity higher than 99.9% 2 CO 3 And (5) producing the product.
Further, the lithium slag used in the step (1) is produced in the production process of extracting lithium from spodumene or lepidolite ore, extracting lithium from salt lake brine or underground brine or butyl lithium.
Further, the main components and contents of the lithium slag are as follows: 8 to 12% of Li oxide or compound, mg (OH) 2 15～20％、CaSO 4 25～30％、SiO 2 35～40％、B 2 O 3 3～5％。
Further, oxides or compounds of Li include LiOH, liCl, li 2 CO 3 Or Li 2 O。
Further, the filter residue obtained in the step (3) is Li 2 CO 3 、MgCO 3 、CaCO 3 、SiO 2 And B 2 O 3 A mixture of (a).
Further, the carbonate used in the step (2) is any one or two of potassium carbonate and sodium carbonate.
Further, the filtrate obtained in the step (3) may be used for dissolving the powder after mechanical grinding at the next preparation of lithium carbonate.
Has the advantages that:
1. according to the invention, the lithium carbonate product is produced by taking the lithium extracted from spodumene or lepidolite ore, the lithium extracted from salt lake brine or underground brine and the lithium slag generated in the butyl lithium production process as main raw materials, so that expensive and scarce lepidolite is replaced, the problem of high cost when LiOH is directly used as a raw material is solved, and the production cost of lithium carbonate is reduced.
2. The production process disclosed by the invention has the advantages of easiness in controlling solid-liquid reaction and liquid-liquid reaction, no need of complex equipment, strong operability, simple process, high product purity of 99.9%, impurity content: na (Na)<0.014％，Ca<0.0018％，K<0.003％，Mg<0.033％，SO 4 2- <0.041 percent, improves the market competitiveness.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood 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 any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
The invention provides a preparation method of low-cost battery-grade lithium carbonate, which takes lithium extracted from spodumene or lepidolite ore, lithium extracted from salt lake brine or underground brine and lithium slag generated in the production process of butyl lithium as raw materials, wherein the lithium slag comprises the following main components in percentage by weight: liOH, liCl, li 2 CO 3 Or Li 2 O：8～12％，Mg(OH) 2 :15～20％，CaSO 4 :25～30％，SiO 2 :35～40％，B 2 O 3 3-5 percent, generates lithium carbonate, carbon, calcines and other processes through the processes of crushing, screening, uniformly mixing with carbonate, mechanical grinding, depositing and the like, and has the characteristics of stable process, low cost and the like.
A preparation method of low-cost battery-grade lithium carbonate comprises the following steps:
(1) Placing the lithium slag into a jaw crusher or a vertical crusher for coarse crushing, and performing ball milling and screening on the coarse crushed lithium slag to ensure that the lithium slag with the granularity lower than 100 meshes accounts for more than 80% of the total lithium slag;
(2) And uniformly mixing the sieved lithium slag and carbonate according to the mass ratio of 5:1, and mechanically and fully grinding in a planetary ball mill. Wherein the carbonate is one or two of potassium carbonate and sodium carbonate. The chemical reaction that takes place in this step (as exemplified with sodium carbonate only):
2LiCl+Na 2 CO 3 ＝Li 2 CO 3 +2NaCl；
(3) Adding deionized water into the ground powder in the step (2) to obtain a suspension with a solid-to-liquid ratio of 1 (1-2), reacting for 1h at 90-95 ℃, filtering by using a suction filter, wherein filter residue is Li 2 CO 3 、MgCO 3 、CaCO 3 、SiO 2 And B 2 O 3 The filtrate can be used for dissolving and grinding the powder for the next time. The chemical reaction that takes place in this step:
Li 2 O+H 2 O＝2LiOH；
2LiOH+Na 2 CO 3 ＝Li 2 CO 3 +2NaOH；
(4) And adding deionized water into the filter residue obtained in the third step at room temperature to obtain a suspension with the solid-to-liquid ratio of 1 (2-3), introducing excessive carbon dioxide into the suspension, and carrying out main chemical reaction in the step:
Li 2 CO 3 +CO 2 +H 2 O＝2LiHCO 3 ；
CaCO 3 +CO 2 +H 2 O＝Ca(HCO 3 ) 2 ；
MgCO 3 +CO2+H 2 O＝Mg(HCO 3 ) 2 ；
(5) Filtering the turbid liquid obtained in the fourth step, removing filter residues, heating the filtrate to 70-75 ℃, then vacuumizing, maintaining the vacuum degree at 0.2-0.25 atm, and keeping the vacuum degree for 1 hour, wherein the main chemical reaction in the step is as follows:
2LiHCO 3 ＝Li 2 CO 3 +CO 2 +H 2 O；
Ca(HCO 3 ) 2 ＝CaCO 3 +CO 2 +H 2 O；
CaCO 3 ＝CaO+CO 2 ；
Mg(HCO 3 ) 2 ＝MgCO 3 +CO 2 +H 2 O；
MgCO 3 ＝MgO+CO 2 ；
(6) And (5) carrying out suction filtration on the solid-liquid mixture obtained in the step (5) to obtain Li 2 CO 3 Washing the crude product with deionized water to remove Li 2 CO 3 Soluble impurity ions in the crude product and drying at 100-105 deg.C for 2h to obtain Li with purity higher than 99.9% 2 CO 3 And (5) producing the product.
Example 1
A low-cost lithium carbonate preparation method comprises the following steps:
(1) Respectively weighing a certain amount of lithium slag and sodium carbonate for later use;
(2) Coarsely crushing the lithium slag into particles with the particle size of less than 10mm by a crusher; ball-milling in a ball mill for 4h, and then sieving with a 100-mesh sieve;
(3) Adding sodium carbonate into the sieved lithium slag (-100 meshes is not less than 80%) of the step (2) according to the mass of the lithium slag and the sodium carbonate 5:1, and performing ball milling for 4 hours in a planetary ball mill;
(4) Adding deionized water into the powder after ball milling in the step (3) to obtain a suspension of 1:1 in solid-to-liquid ratio, reacting for 1h at 90-95 ℃, and filtering by a suction filter to obtain filter residue;
(5) Adding deionized water into the filter residue obtained in the step (4) to obtain a suspension of 1:2 in solid-to-liquid ratio, and introducing excessive carbon dioxide into the suspension;
(6) Filtering the suspension obtained in the step (5), removing filter residues, heating the filtrate to 75 ℃, and then vacuumizing, wherein the vacuum degree is maintained at 0.2atm for 1h;
(7) And (4) carrying out suction filtration on the solid-liquid mixture obtained in the step (6) to obtain Li 2 CO 3 Washing the crude product with deionized water to remove Li 2 CO 3 Soluble impurity ions in the crude product are dried for 2 hours at 100 ℃ to obtain the product with the purity higher than that of Li 2 CO 3 And (5) producing the product.
For the obtained Li 2 CO 3 Analysis of the composition of the product, li obtained in this example 2 CO 3 The product indexes are as follows: li 2 CO 3 ：99.9％，Na：0.014％，Ca：0.001％，K：0.001％，Mg：0.023％，SO 4 2- ：0.024％。
Example 2
A low-cost lithium carbonate preparation method comprises the following steps:
(1) Respectively weighing a certain amount of lithium slag and potassium carbonate for later use;
(2) Coarsely crushing the lithium slag into particles with the particle size of less than 10mm by a crusher; ball-milling in a ball mill for 4h, and then sieving with a 100-mesh sieve;
(3) Adding potassium carbonate into the sieved lithium slag (-100 meshes is not less than 80%) of the step (2) according to the mass of the lithium slag and the potassium carbonate 5:1, and performing ball milling for 4 hours in a planetary ball mill;
(4) Adding deionized water into the powder obtained after grinding in the step (3) to obtain a suspension of 1:2 in solid-to-liquid ratio, reacting for 1h at 95 ℃, and filtering by a suction filter to obtain filter residue for later use;
(5) Adding deionized water into the filter residue obtained in the step (4), wherein the solution solid-liquid ratio is 1:3, and introducing excessive carbon dioxide into the solution;
(6) Filtering the suspension obtained in the step (5), removing filter residues, heating the filtrate to 75 ℃, and then vacuumizing, wherein the vacuum degree is maintained at 0.25atm for 1h;
(7) And (4) carrying out suction filtration on the solid-liquid mixture obtained in the step (6) to obtain Li 2 CO 3 Washing the crude product with deionized water to remove Li 2 CO 3 In the crude productAnd drying at 105 deg.C for 2h to obtain impurity ions with purity higher than that of Li 2 CO 3 And (5) producing the product.
For the obtained Li 2 CO 3 Analysis of the composition of the product, li obtained in this example 2 CO 3 The product indexes are as follows: li 2 CO 3 ：99.9％，Na：0.011％，Ca：0.001％，K：0.003％，Mg：0.024％，SO 4 2- ：0.022％。
In conclusion, the preparation method provided by the invention adopts low-cost lithium slag for preparation, is simple to operate, and can obtain a high-purity lithium carbonate product.
The foregoing is merely a preferred embodiment of the invention and is not to be construed as limiting the invention in any way. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (3)
1. A preparation method of low-cost battery-grade lithium carbonate is characterized by comprising the following steps:
(1) Coarse crushing, ball milling and screening the lithium slag to ensure that the lithium slag with the granularity lower than 100 meshes accounts for more than 80 percent of the total lithium slag; the lithium slag comprises the following main components in percentage by weight: oxide or Compound of Li 8 to 12%, mg (OH) 2 15~20%、CaSO 4 25~30%、SiO 2 35~40%、B 2 O 3 3~5%; oxides or compounds of Li including LiOH, liCl, li 2 CO 3 Or Li 2 O；
(2) Uniformly mixing the sieved lithium slag and carbonate according to the mass ratio of 5:1, and then fully mechanically grinding;
(3) And (3) adding deionized water into the powder obtained after mechanical grinding in the step (2) to obtain a powder with a solid-to-liquid ratio of 1: (1~2) at 90-95 deg.C for 1h, filtering with suction filter to obtain filter residue, which is Li 2 CO 3 、MgCO 3 、CaCO 3 、SiO 2 And B 2 O 3 A mixture of (a);
(4) Step (3) at room temperatureAnd adding deionized water into the obtained filter residue to obtain a mixture with a solid-to-liquid ratio of 1: (2~3) and introducing excess CO into the suspension 2 ；
(5) Filtering the suspension obtained in the step (4), removing filter residues, heating the filtrate to 70-75 ℃, and then vacuumizing, wherein the vacuum degree is maintained at 0.2-0.25atm for 1h;
(6) And (5) carrying out suction filtration on the solid-liquid mixture obtained in the step (5) to obtain Li 2 CO 3 Washing the crude product with deionized water to remove Li 2 CO 3 Soluble impurity ions in the crude product, and drying for 2h at 100-105 ℃ to obtain Li with the purity higher than 99.9% 2 CO 3 Producing a product;
wherein the lithium slag used in the step (1) is produced in the production process of extracting lithium from spodumene or lepidolite ore, extracting lithium from salt lake brine or underground brine or butyl lithium.
2. The method for preparing low-cost battery-grade lithium carbonate according to claim 1, wherein the method comprises the following steps: the carbonate used in the step (2) is one or two of potassium carbonate and sodium carbonate.
3. The method for preparing low-cost battery-grade lithium carbonate according to claim 1, wherein the method comprises the following steps: the filtrate obtained in step (3) may be used to dissolve the mechanically ground powder in the next preparation of lithium carbonate.
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Effective date of registration: 20230627 Address after: Room A826, No. 1718 Airport Road, Yuncheng Street, Baiyun District, Guangzhou City, Guangdong Province, 510080 (self declared) Patentee after: Guangzhou Lingke Intellectual Property Operation Co.,Ltd. Address before: 471000 No. 48, Xiyuan Road, Jianxi District, Henan, Luoyang Patentee before: HENAN University OF SCIENCE AND TECHNOLOGY Effective date of registration: 20230627 Address after: 411400 Building 01, Kexinting, Xinxiang Road Office, Xiangxiang, Xiangtan, Hunan Province Patentee after: Hunan Xiangli New Materials Co.,Ltd. Address before: Room A826, No. 1718 Airport Road, Yuncheng Street, Baiyun District, Guangzhou City, Guangdong Province, 510080 (self declared) Patentee before: Guangzhou Lingke Intellectual Property Operation Co.,Ltd. |