CN108423694B - Method for producing lithium sulfate mother liquor or lithium carbonate by taking spodumene as raw material - Google Patents
Method for producing lithium sulfate mother liquor or lithium carbonate by taking spodumene as raw material Download PDFInfo
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- CN108423694B CN108423694B CN201711444186.XA CN201711444186A CN108423694B CN 108423694 B CN108423694 B CN 108423694B CN 201711444186 A CN201711444186 A CN 201711444186A CN 108423694 B CN108423694 B CN 108423694B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention relates to a method for producing lithium sulfate mother liquor or lithium carbonate by taking spodumene as a raw material, belonging to the technical field of extracting lithium from spodumene. The invention aims to provide a method for producing lithium sulfate mother liquor by taking spodumene as a raw material with low cost. According to the method, the spodumene is calcined, transformed and taken out of the furnace, and is directly crushed without cooling, and then the crushed spodumene powder waste heat is utilized to carry out sulfation in the heat preservation device, roasting is not needed during sulfation, so that energy is greatly saved, the production cost of lithium salt is reduced, a large-scale sulfation kiln is not needed, the production efficiency is ensured, the production line is simplified, and the equipment cost is reduced. The method has the advantages of high lithium recovery rate and low cost, and is suitable for industrial mass production.
Description
Technical Field
The invention relates to a method for producing lithium sulfate mother liquor or lithium carbonate by taking spodumene as a raw material, belonging to the technical field of extracting lithium from spodumene.
Background
In recent years, lithium and compounds thereof are used as an important new energy material, and have important significance for development of energy industries such as lithium batteries and nuclear power. Lithium is widely distributed in nature, and exists in rocks, soil, bittern and seawater. At present, the extraction of lithium mainly comprises two directions of extracting lithium from brine and extracting lithium from ore, wherein the extraction of lithium from ore is an important source of lithium and lithium salt in China. Spodumene is of great interest as one of the major lithium mineral resources.
At present, the main production processes for extracting lithium from spodumene comprise a lime sintering method and a sulfuric acid method, wherein the sulfuric acid method is the main method used at present, and the main process route of the sulfuric acid method is as follows: alpha-spodumene is converted into beta-spodumene through high-temperature roasting of crystal form, and then ore grinding is carried out after cooling, then the beta-spodumene is mixed with sulfuric acid, and the mixture is acidified and roasted to produce soluble lithium sulfate, lithium sulfate mother liquor is obtained through leaching, and then different lithium salt products are produced through measures such as evaporation, concentration and impurity removal.
For example, the invention patent with application number 201080065025.X discloses a method for manufacturing lithium carbonate, which comprises the following steps: calcining the alpha-spodumene ore or concentrate to produce beta-spodumene; then cooling and ball-milling, mixing the mixture with sulfuric acid, transferring the mixture into a sulfation kiln, and sulfating beta-spodumene at high temperature; passing the sulfated β -spodumene to a leaching step wherein lithium sulfate is leached in water; then a series of impurity removal measures are carried out to finally obtain precipitated lithium carbonate and sodium sulfate mother liquor.
For another example, the invention patent with application number 201110000790.X discloses a method for producing lithium carbonate and lithium hydroxide, which comprises the following steps of a. spodumene concentrate: roasting at 1050-1100 ℃, cooling, finely grinding, adding 98% concentrated sulfuric acid, acidizing and roasting at 250-300 ℃, extracting by a wet method to remove calcium and magnesium impurities, evaporating, concentrating, and filter-pressing to obtain a lithium sulfate solution, and then preparing a lithium carbonate mother solution to obtain lithium carbonate; the lithium hydroxide can also be obtained by adding barium hydroxide into the lithium carbonate mother liquor.
The invention patent with application number 201610364357.7 discloses a new process for producing lithium salt by a sulfuric acid method, which comprises the following steps: roasting the spodumene concentrate, and cooling to obtain spodumene calcine; grinding the spodumene calcine to obtain spodumene mineral powder; adding sulfuric acid into spodumene mineral powder, and roasting to obtain acid clinker; adding calcium carbonate into the acid clinker to obtain a mixture, adding water into the mixture, and filtering to obtain a lithium sulfate leaching solution; and removing impurities by a microfiltration membrane, adding soda ash and other measures to prepare a finished lithium carbonate product.
The above patents all adopt the common sulfuric acid method to extract lithium from spodumene, and prepare products such as lithium carbonate, lithium hydroxide and the like. With the rising price of spodumene raw materials and the reduction of product price, the profit of ore lithium extraction manufacturers is very thin, and the lithium industry faces a serious challenge. How to reduce the cost of extracting lithium from spodumene becomes an important subject of extracting lithium from lithium ore. In recent years, China's ore lithium extraction production enterprises have conducted a great deal of research on spodumene lithium extraction processes to reduce cost, but the effect is not good enough, and the production still continues to use the traditional sulfuric acid process and traditional equipment.
The traditional sulfuric acid process equipment comprises a calcining furnace, a cooler, a crusher, a mixer, a sulfating kiln and other key equipment, the production line has a wide occupied area, for example, the production line for processing seventy thousand tons of spodumene annually occupies 1800 square meters, the cooler occupies 200 square meters, the crusher occupies 300 square meters, the mixer occupies 200 square meters and the sulfating kiln occupies 2700 square meters, so that the whole production line has larger equipment, wide occupied area and high equipment cost. The early stage of production is relatively high in investment and relatively high in cost.
Disclosure of Invention
Aiming at the defects, the technical problem solved by the invention is to provide a low-cost method for producing lithium sulfate mother liquor by taking spodumene as a raw material.
The method for producing the lithium sulfate mother liquor by taking spodumene as a raw material comprises the following steps:
a. and (3) calcining: calcining the alpha-spodumene in a calcining furnace to convert the alpha-spodumene into beta-spodumene, and discharging the beta-spodumene from the furnace;
b. crushing: directly crushing the discharged beta-spodumene without cooling by a cooler to obtain spodumene powder;
c. acidifying: uniformly mixing the spodumene powder and sulfuric acid, and then, keeping the temperature for 20-30 min by using the waste heat of the spodumene powder without heating in a heat preservation device to obtain acid clinker;
d. leaching: and leaching the acid clinker with water, and filtering to obtain a lithium sulfate mother liquor.
Preferably, in the step a, the calcining temperature is 950-1100 ℃, and the calcining time is 0.5-2 h.
Further preferably, the temperature of the beta-spodumene discharged from the furnace is 600-900 ℃.
Preferably, in the step b, the particle size of the spodumene powder is 3mm or less.
Preferably, in the step c, the ratio of the spodumene powder to the sulfuric acid is 1: 0.14-0.3 g/mL.
Further preferably, in the step c, the temperature of the mixed slurry of spodumene powder and sulfuric acid in the heat-insulating device is 250 ℃ or higher.
Preferably, the calcining furnace in the step a adopts a rotary kiln, the rotary kiln comprises a cold end provided with a feeding port and a hot end provided with a discharging port, the hot end of the rotary kiln is inserted into a coal injection pipe in the rotary kiln, and a distance is reserved between a nozzle of the coal injection pipe and the discharging port along the axial direction of the rotary kiln, so that a cooling section is formed between the discharging port and the nozzle, and the temperature of the obtained beta-spodumene is 600-900 ℃.
The invention solves the second technical problem by providing a method for producing lithium carbonate by taking spodumene as a raw material.
The method for producing lithium carbonate by taking spodumene as a raw material comprises the step of producing the lithium sulfate mother liquor by taking spodumene as a raw material.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, after spodumene is calcined out of the furnace, the spodumene is directly crushed at high temperature without cooling, and then the crushed spodumene powder waste heat is utilized to carry out sulfation in a heat preservation device, roasting is not needed during sulfation, so that energy is greatly saved, the production cost of lithium salt is reduced, a large-scale sulfation kiln is not needed, the production efficiency is ensured, the production line is simplified, and the equipment cost is reduced.
The method has the advantages of high lithium recovery rate and low cost, and is suitable for industrial mass production.
Drawings
Fig. 1 is a schematic view of the structure of a rotary kiln of the present invention.
Wherein, the method comprises the steps of 1-rotary kiln, 2-coal injection pipe, 3-cooling section and 4-discharge hole.
Detailed Description
The method for producing the lithium sulfate mother liquor by taking spodumene as a raw material comprises the following steps:
a. and (3) calcining: calcining the alpha-spodumene in a calcining furnace to convert the alpha-spodumene into beta-spodumene, and discharging the beta-spodumene from the furnace;
b. crushing: directly crushing the discharged beta-spodumene without cooling by a cooler to obtain spodumene powder;
c. acidifying: uniformly mixing the spodumene powder and sulfuric acid, and then, keeping the temperature for 20-30 min by using the waste heat of the spodumene powder without heating in a heat preservation device to obtain acid clinker;
d. leaching: and leaching the acid clinker with water, and filtering to obtain a lithium sulfate mother liquor.
The method for producing the lithium sulfate mother liquor by taking spodumene as the raw material utilizes the waste heat of spodumene powder to carry out sulfation, the sulfation is only carried out in a simple heat preservation device, a production line for treating seventy thousand tons of spodumene is treated every year, the crushing, acidifying and heat preservation devices only occupy 120 square meters, the occupied area is small, the cost is low, the equipment cost and the early-stage investment cost are reduced, the energy is saved, and the production cost is reduced.
Spodumene has 3 crystal forms, namely, the natural alpha-spodumene, namely the raw material spodumene of the invention can become a stable variant after being heated to a certain temperature, and is beta-spodumene, and the beta-spodumene can be converted into gamma-spodumene at higher temperature. Alpha-spodumene is a monoclinic crystal, has a compact structure and high chemical inertia, hardly reacts with various acids and bases except hydrofluoric acid, and needs to be transformed into beta-spodumene of a tetragonal crystal system through crystal transformation roasting in order to extract lithium from natural spodumene, so that the lithium can be extracted by various reactions with acid and bases after the chemical activity is increased. Therefore, the calcination in step a is to transform spodumene, facilitating the later elution of lithium. The calcination is performed on the basis of fully converting the alpha-spodumene into the beta-spodumene, preferably, the calcination temperature is 950-1100 ℃, and the calcination time is 0.5-2 h.
In order to facilitate the smooth proceeding of the subsequent crushing, the temperature of the beta-spodumene discharged from the furnace is preferably controlled to be 600-900 ℃.
The b step is a crushing of beta-spodumene in order to better sulphate the lithium, which is carried out directly after the calcination discharge, without cooling. Therefore, the temperature of spodumene is 600-900 ℃ during crushing. The crushing in the step b can adopt conventional high-temperature-resistant crushing equipment. Preferably, the particle size of the crushed spodumene powder is 3mm or less.
Step c, reacting the spodumene powder with sulfuric acid to generate lithium sulfate, wherein the reaction principle is as follows:
β-LiO2·Al2O3·4SiO2+H2SO4→Li2SO4+H2O·Al2O3·4SiO2
in the conventional sulfuric acid method for extracting lithium from spodumene, the step needs to be heated and roasted in a kiln so as to ensure the reaction temperature. The inventor of the invention discovers that the spodumene is directly crushed after being calcined and discharged, the temperature of the spodumene is about 600-900 ℃ during crushing, sulfuric acid is immediately added into the crushed spodumene for uniformly mixing after the crushing, and then the mixture is heated in a heat preservation device without heating, and the heat preservation is carried out for 20-30 min by utilizing the waste heat of the spodumene, so that the sulfation of the spodumene can be carried out without an external heating source, and the lithium sulfate is obtained. Therefore, the energy can be saved, the production cost can be reduced, a sulfating kiln can be omitted, the process can be realized by simple heat preservation equipment, the equipment cost can be greatly reduced, the occupied area of the equipment is reduced, and the whole production line is simplified.
In the step c, the sulfuric acid can be commercially available, and preferably, the material-to-liquid ratio of the spodumene powder to the sulfuric acid is 1: 0.14-0.3 g/mL.
For better sulfation, it is preferable that the temperature of the material in the holding device in step c is 250 ℃ or higher.
And d, leaching in the step d is a conventional step, and leaching lithium sulfate by using water by utilizing the property that the lithium sulfate is dissolved in the water to obtain lithium sulfate mother liquor.
The lithium sulfate mother liquor can be prepared into lithium salt products by the existing method, such as lithium carbonate, lithium chloride or lithium hydroxide and other products.
The calcining furnace of the present invention can be used for calcining with a conventional, preferably, rotary kiln. As shown in fig. 1, spodumene enters the rotary kiln 1 from a feed inlet at the cold end of the rotary kiln 1 to be calcined at high temperature; the calcined spodumene is driven by the rotary kiln 1 to be cooled through the cooling section 3, and then is directly discharged into a feeding port of a high-temperature-resistant crusher capable of crushing materials with higher temperature through a discharging port 4 to be crushed.
The invention also provides a method for producing lithium carbonate by taking spodumene as a raw material.
The method for producing lithium carbonate by taking spodumene as a raw material comprises the step of producing the lithium sulfate mother liquor by taking spodumene as a raw material. The lithium sulfate mother liquor is produced by the method for producing the lithium sulfate mother liquor by taking spodumene as the raw material, and then lithium carbonate can be produced by adopting conventional steps, for example, the lithium sulfate mother liquor is subjected to impurity removal, carbonization and purification to obtain lithium carbonate.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
The lithium sulfate mother liquor is produced by adopting the following method:
a. and (3) calcining: calcining the alpha-spodumene in a calcining furnace to convert the alpha-spodumene into beta-spodumene, and discharging from the furnace, wherein the temperature of the beta-spodumene is 600 ℃ during discharging.
b. Crushing: and directly crushing the discharged beta-spodumene in high-temperature resistant crushing equipment until the particle size is less than 3mm to obtain spodumene powder.
c. Acidifying: uniformly mixing the spodumene powder and 98 wt% concentrated sulfuric acid according to the material-liquid ratio of 1:0.14g/mL, transferring the mixture into a heat preservation device, preserving the temperature of slurry in the heat preservation device for 30min at the moment, and carrying out sulfation by using the waste heat of the spodumene powder without heating to obtain acid clinker;
d. leaching: and leaching the acid clinker with water, and filtering to obtain a lithium sulfate mother liquor.
By adopting the method, 3700kJ is needed for treating each ton of spodumene, the treatment cost is 273 yuan/ton, and the recovery rate of lithium is 98.3%. The recovery rate of lithium in the invention is the lithium content in the lithium sulfate mother liquor divided by the lithium content in alpha-spodumene.
Example 2
The lithium sulfate mother liquor is produced by adopting the following method:
a. and (3) calcining: calcining the alpha-spodumene in a calcining furnace to convert the alpha-spodumene into beta-spodumene, and discharging from the furnace, wherein the calcining temperature is 1100 ℃, the calcining time is 0.5h, and the temperature of the beta-spodumene is 900 ℃ when discharging from the furnace.
b. Crushing: and directly crushing the discharged beta-spodumene in high-temperature resistant crushing equipment until the particle size is less than 3mm to obtain spodumene powder.
c. Acidifying: uniformly mixing spodumene powder and 98 wt% concentrated sulfuric acid according to the material-liquid ratio of 1:0.3g/mL, transferring into a heat preservation device, preserving heat for 20min in a heat preservation device at the temperature of 300 ℃, and sulfating by using the waste heat of the spodumene powder to obtain acid clinker;
d. leaching: and leaching the acid clinker with water, and filtering to obtain a lithium sulfate mother liquor.
By adopting the method, 3700kJ is needed for treating each ton of spodumene, the treatment cost is 360 Yuan/ton, and the recovery rate of lithium is 98.4%.
Example 3
The lithium sulfate mother liquor is produced by adopting the following method:
a. and (3) calcining: calcining the alpha-spodumene in a calcining furnace to convert the alpha-spodumene into beta-spodumene, and discharging the beta-spodumene from the furnace, wherein the temperature of the beta-spodumene is 800 ℃ during discharging.
b. Crushing: and directly crushing the discharged beta-spodumene in high-temperature resistant crushing equipment until the particle size is less than 3mm to obtain spodumene powder.
c. Acidifying: uniformly mixing the spodumene powder and 98 wt% concentrated sulfuric acid according to the material-liquid ratio of 1:0.2g/mL, transferring the mixture into a heat preservation device, preserving the temperature of slurry in the heat preservation device for 30min at the moment, and carrying out sulfation by using the waste heat of the spodumene powder without heating to obtain acid clinker;
d. leaching: and leaching the acid clinker with water, and filtering to obtain a lithium sulfate mother liquor.
By adopting the method, 3700kJ is needed for treating each ton of spodumene, the treatment cost is 310 yuan/ton, and the recovery rate of lithium is 98.4%. Low recovery cost and high yield.
Example 4
The lithium sulfate mother liquor is produced by adopting the following method:
a. and (3) calcining: calcining the alpha-spodumene in a calcining furnace to convert the alpha-spodumene into beta-spodumene, and discharging from the furnace, wherein the calcining temperature is 950 ℃, the calcining time is 2 hours, and the temperature of the beta-spodumene is 800 ℃ during discharging.
b. Crushing: and directly crushing the discharged beta-spodumene in high-temperature resistant crushing equipment until the particle size is less than 3mm to obtain spodumene powder.
c. Acidifying: uniformly mixing spodumene powder and 98 wt% concentrated sulfuric acid according to the material-liquid ratio of 1:0.2g/mL, transferring into a heat preservation device, preserving heat for 25min in a heat preservation device at the slurry temperature of 280 ℃, and sulfating by using the waste heat of the spodumene powder to obtain acid clinker;
d. leaching: and leaching the acid clinker with water, and filtering to obtain a lithium sulfate mother liquor.
e. Preparing lithium carbonate: and removing impurities from the lithium sulfate mother liquor, and adding sodium carbonate to obtain lithium carbonate precipitate.
By adopting the method, 4200kJ is needed for treating each ton of spodumene, the treatment cost is 340 yuan/ton, and the recovery rate of lithium is 98.4%.
Comparative example 1
The lithium sulfate mother liquor is produced by adopting the following method:
a. and (3) calcining: calcining the alpha-spodumene in a calcining furnace to convert the alpha-spodumene into beta-spodumene, discharging from the furnace, wherein the calcining temperature is 950 ℃, the calcining time is 2 hours, and cooling to the normal temperature after discharging from the furnace.
b. Ball milling: and (3) crushing the cooled spodumene to below 80 meshes to obtain spodumene powder.
c. Acidifying: uniformly mixing spodumene powder and 98 wt% concentrated sulfuric acid according to the feed-liquid ratio of 1:0.2g/mL, and roasting at 280 ℃ for 25min to obtain acid clinker;
d. leaching: and leaching the acid clinker with water, and filtering to obtain a lithium sulfate mother liquor.
By adopting the method, 5400kJ is needed for treating each ton of spodumene, the treatment cost is 410 yuan/ton, and the recovery rate of lithium is 98.4%.
In conclusion, compared with the prior art, the method provided by the invention can save the cost by 50-140 yuan for treating each ton of spodumene, and can save the production cost by 350-960 ten thousand yuan for one year by taking a production line for treating seven ten thousand tons per year as an example, so that the cost for extracting lithium from spodumene is greatly reduced.
Claims (10)
1. The method for producing the lithium sulfate mother liquor by taking spodumene as a raw material is characterized by comprising the following steps of:
a. and (3) calcining: calcining the alpha-spodumene in a calcining furnace to convert the alpha-spodumene into beta-spodumene, and discharging the beta-spodumene from the furnace;
b. crushing: directly crushing the discharged beta-spodumene without cooling by a cooler to obtain spodumene powder;
c. acidifying: uniformly mixing the spodumene powder and sulfuric acid, and then, keeping the temperature for 20-30 min by using the waste heat of the spodumene powder without heating in a heat preservation device to obtain acid clinker;
d. leaching: leaching the acid clinker with water, and filtering to obtain a lithium sulfate mother liquor;
and c, adopting a rotary kiln as the calcining furnace in the step a, wherein the rotary kiln comprises a cold end provided with a feeding port and a hot end provided with a discharging port, the hot end of the rotary kiln is inserted into a coal injection pipe in the rotary kiln, and a distance is reserved between a nozzle of the coal injection pipe and the discharging port along the axial direction of the rotary kiln, so that a cooling section is formed between the discharging port and the nozzle, and the temperature of the obtained beta-spodumene is 600-900 ℃.
2. The method for producing lithium sulfate mother liquor by using spodumene as a raw material according to claim 1, which is characterized in that: in the step a, the calcining temperature is 950-1100 ℃, and the calcining time is 0.5-2 h.
3. The method for producing lithium sulfate mother liquor using spodumene as a raw material according to claim 1 or 2, characterized in that: in the step b, the particle size of the spodumene powder is less than 3 mm.
4. The method for producing lithium sulfate mother liquor using spodumene as a raw material according to claim 1 or 2, characterized in that: in the step c, the ratio of the spodumene powder to the sulfuric acid is 1: 0.14-0.3 g/mL.
5. The method for producing lithium sulfate mother liquor by using spodumene as a raw material according to claim 3, wherein the method comprises the following steps: in the step c, the ratio of the spodumene powder to the sulfuric acid is 1: 0.14-0.3 g/mL.
6. The method for producing lithium sulfate mother liquor using spodumene as a raw material according to claim 1 or 2, characterized in that: in the step c, the temperature of the mixed slurry of the spodumene powder and the sulfuric acid in the heat preservation device is more than 250 ℃.
7. The method for producing lithium sulfate mother liquor by using spodumene as a raw material according to claim 3, wherein the method comprises the following steps: in the step c, the temperature of the mixed slurry of the spodumene powder and the sulfuric acid in the heat preservation device is more than 250 ℃.
8. The method for producing lithium sulfate mother liquor by using spodumene as a raw material according to claim 4, wherein the method comprises the following steps: in the step c, the temperature of the mixed slurry of the spodumene powder and the sulfuric acid in the heat preservation device is more than 250 ℃.
9. The method for producing lithium sulfate mother liquor by using spodumene as a raw material according to claim 5, wherein the method comprises the following steps: in the step c, the temperature of the mixed slurry of the spodumene powder and the sulfuric acid in the heat preservation device is more than 250 ℃.
10. A method for producing lithium carbonate from spodumene, comprising the step of producing a lithium sulfate mother liquor from spodumene as claimed in any one of claims 1 to 9.
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| CN110395749A (en) * | 2019-08-09 | 2019-11-01 | 山东科技大学 | A method of lithium chloride is prepared using the displacement reaction electrodialysis of four compartments |
| CN112661175A (en) * | 2021-01-21 | 2021-04-16 | 广西天源新能源材料有限公司 | Lithium carbonate preparation method based on combination of salt lake ore, lithium polymer and spodumene |
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