CN107964597B - Method for extracting alkali metal by treating lepidolite - Google Patents
Method for extracting alkali metal by treating lepidolite Download PDFInfo
- Publication number
- CN107964597B CN107964597B CN201711243215.6A CN201711243215A CN107964597B CN 107964597 B CN107964597 B CN 107964597B CN 201711243215 A CN201711243215 A CN 201711243215A CN 107964597 B CN107964597 B CN 107964597B
- Authority
- CN
- China
- Prior art keywords
- lepidolite
- agent
- alkali metal
- reconstruction
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a method for extracting alkali metal by treating lepidolite, which comprises the following steps: uniformly mixing the mechanically activated lepidolite with a reconstruction agent to obtain a mixture, uniformly mixing the mixture with an acidic activating agent, and reacting for 1-4 hours at 50-100 ℃; then heating to 500-800 ℃, reacting for 10-60 s, and cooling to 150-250 ℃ to obtain reconstructed clinker; and finally, adding the reconstructed clinker into an alkaline leaching agent, leaching alkali metal ions, and synchronously removing impurities through solid-liquid separation to obtain a lithium salt solution rich in alkali metal and solid impurities. The method of the invention fully utilizes potassium, sodium, aluminum elements and fluorine elements in the lepidolite to generate acid-insoluble cryolite as a fluxing agent, utilizes sodium and potassium salts in the mica neutralization system as a reconstruction agent, does not need to additionally add potassium, sodium, aluminum and other raw materials in the whole process, and has the characteristics of short process, low reconstruction temperature, low energy consumption and high alkali metal recovery rate.
Description
Technical Field
The invention belongs to the technical field of mineral processing, and particularly relates to a method for extracting alkali metal by treating a lepidolite mineral raw material.
Background
At present, the lithium-containing minerals are more, and spodumene (Li) is the main one with industrial value2O·Al2O3·4SiO2) Lepidolite KLi1.5Al1.5[AlSi3O10](OH,F)2Petalite (Li)2O·Al2O3·8SiO2) Phosphorus lepidolite LiAl [ PO ]4](OH, F) and lepidolite K (Li, Al, Fe) [ AlSi3O10](OH,F)2. Meanwhile, salt lake brine is an important source for extracting lithium, because the cost for extracting lithium from brine is low, a plurality of manufacturers exist at present, but because the impurity content of Mg and the like in brine is high, impurity removal in the later period is complicated, the product purity is not high, and along with the increase of lithium demand, the lithium extraction from ores is favored by some manufacturers and starts to produce gradually, so that the process for extracting lithium from ores is gradually mature.
Lithium carbonate is an important chemical raw material, and with the key support of the state on lithium battery materials, lithium batteries are widely applied in the field of high-energy green energy, the demand for lithium carbonate is continuously increased at home and abroad, and the price rises gradually. Rb and Cs are applied to the fields of photocatalysis and military industry due to unique photoelectric effects, and Rb has no single ore which can be exploited, has scarce resources and can not meet the requirements far away, so how to comprehensively develop and utilize lepidolite resources has important economic and strategic significance.
The liriot lepidolite ore in Jiangxi Yichun contains various valuable metal and nonmetal elements such as Li, Na, K, Rb, Cs, Al, F and the like, and has great economic value, the content of Li2O in the lepidolite ore is 4-5 wt%, which is second to 6-8 wt% of spodumene, the content of K2O can be as high as 8.5 wt%, and the content of Rb can reach 1-1.5 wt%, and Rb has great mining value because Rb does not find an ore existing independently so far, so that the lepidolite lithium extraction has great favorable resource advantages.
The prior method for treating lepidolite ore mainly comprises the traditional limestone roasting method, the sulfuric acid method, the sulfate method, the chloridizing roasting and pressure cooking method and the like. Limestone roasting method, chlorination roasting method, traditional sulfuric acid method, etc. all adopt the way of carrying on ore phase reconstruction by high-temperature sintering, because its energy consumption is high, the material flow is great, alkali metal extraction rate such as Li is low, resources such as valuable metals rubidium and cesium can not be fully utilized, reflect advantage and value that the lepidolite ore resource can not be utilized; the sulfuric acid method for extracting alkali metal has large dosage of acid scavenger due to large dosage of sulfuric acid, and the solution mainly contains Al3+And F-Mainly, the separation difficulty with alkali metals is higher, and the amount of the alkali metals attached in the slag is large, so that the recovery rate of the alkali metals in the lepidolite is reduced.
In the research work of developing comprehensive utilization and development of lepidolite resources in Jiangxi province, the lepidolite minerals are generally transformed into corresponding products by adopting ore phase reconstruction and valuable metals for sectional separation to prepare corresponding target products. The reconstruction of the mineral phase is to reconstruct the mineral structure containing valuable components by processing the original mineral, so that the valuable components are converted into a state of being extractable and separable from each other, thereby realizing the high-efficiency separation. For example, chinese patent CN201210080657.4 provides a method for treating lepidolite ore, which aims at the components and mineral structure of lepidolite, designs a specific ore phase reconstruction target to convert alkali metal elements and the like into compounds easily soluble in water, but the method requires high-temperature steam defluorination, and performs ore phase reconstruction after mixing and molding with a reconstruction agent, and has complex procedure and high energy consumption.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology, and provide the method for extracting the alkali metal by processing the lepidolite, the method has the advantages of short flow, low energy consumption, capability of removing impurities and extracting the alkali metal element in one step, and high recovery rate of the alkali metal element.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for processing lepidolite to extract alkali metal comprises the following steps:
uniformly mixing the mechanically activated lepidolite with a reconstruction agent to obtain a mixture, uniformly mixing the mixture with an acidic activating agent, and reacting at 50-100 ℃ for 1-4 h to generate a fluxing auxiliary agent favorable for a boiling reconstruction reaction in the reaction process, so that the temperature of the boiling reconstruction reaction can be reduced, and the energy consumption is saved; heating to 500-800 ℃ for boiling reconstruction reaction for 10-60 seconds to enable alkali metal elements in the lepidolite and a reconstruction agent to perform ion exchange reaction and convert the alkali metal elements into soluble lithium salts and alkali metal salts, combining the reconstruction agent with silicon and aluminum to produce sodium aluminosilicate, potassium aluminosilicate and the like, cooling the materials after reconstruction reaction to 150-250 ℃ to avoid the alkali metal salts from absorbing water, and simultaneously promoting the subsequent leaching reaction by utilizing waste heat to obtain reconstructed clinker; and finally, adding the reconstructed clinker into an alkaline leaching agent, removing impurities such as iron, aluminum, fluorine, nickel, cobalt, manganese, sulfate ions and the like, leaching alkali metal ions, and synchronously removing impurities through solid-liquid separation to obtain an alkali metal-rich lithium salt solution and solid impurities.
In the invention, boiling reconstitution refers to the phenomenon that the reaction material in the reaction system is microspherical slurry, the microspherical slurry is heated and evaporated along with water, and then mineral phase reconstitution reaction is carried out under the condition of boiling and rolling, and the alkali metal in the lepidolite and the reconstitution agent are subjected to ion exchange. The temperature and time of the boiling reconstitution reaction need to be controlled within the scope of the invention, if the temperature and time are lower than the scope of the invention, the reconstitution reaction is incomplete, so that the extraction rate of alkali metal is reduced, and if the temperature and time are beyond the scope of the invention, the alkali metal salt can be subjected to secondary sintering, so that the soluble lithium salt is converted into a difficultly soluble lithium salt or coated, thereby reducing the yield.
The method mainly extracts alkali metal through low-temperature boiling reconstruction of lepidolite, and comprises the process steps of mechanical activation of lepidolite ore, low-temperature material preparation, chemical activation, boiling reconstruction, alkali metal salt dissolution separation and the like. The alkali metal is converted into soluble salt to carry out medium-low temperature ore phase reconstruction, impurities such as fluorine, sulfate radicals and the like which are remained in the dissolved alkali metal salt react with a leaching agent to generate an insoluble complex, reconstructed waste residues exist in the form of aluminosilicate, one-step impurity removal is realized to extract the alkali metal element, the reconstructed waste residues can be directly recycled as the reconstructing agent for recycling or can be directly used as basic raw materials in the building industry, and a novel method for economic and efficient development and utilization is provided for lepidolite treatment.
In the above method, preferably, the reconstituting agent is a sulfate and/or chloride salt of sodium, potassium. Because a large amount of sulfate and/or chloride of sodium and potassium are generated in the activation process and the reconstruction reaction process, in order to avoid bringing other impurities, reduce the material flow flux in the reaction system and realize the recycling of resources, the sulfate and/or chloride of sodium and potassium are added into the method as the reconstruction agent.
In the above method, preferably, the acidic activator is sulfuric acid, hydrochloric acid, nitric acid and/or hydrofluoric acid.
In the above method, the mass ratio of the lepidolite to the restructuring agent is preferably (2 to 5): 1. The mass ratio of the lepidolite to the restructuring agent needs to be controlled within the range of the invention, if the mass ratio is beyond the range of the invention, the addition amount of the restructuring agent is too small, which is not favorable for the full progress of the restructuring reaction, and if the mass ratio is below the range of the invention, the amount of the restructuring agent is excessive, which is not favorable for controlling the cost.
In the method, the mass ratio of the acidic activator to the mixture is preferably (1-3): 1. The mass ratio of the acidic activator to the mixture needs to be controlled within the range of the invention, if the mass ratio of the acidic activator to the mixture exceeds the range of the invention, a part of acidic substances are remained in a reconstruction reaction system due to excessive addition of the acidic activator, corrosion is caused to equipment such as a reconstruction tower, and meanwhile, the cost is increased, if the mass ratio of the acidic activator to the mixture is lower than the range of the invention, the activation degree of the lepidolite is insufficient, and the reconstruction reaction is not facilitated.
In the method, preferably, the alkaline leaching agent is a calcium hydroxide and/or sodium hydroxide solution, and the pH value of the alkaline leaching agent is 10-12. The pH value of the alkaline leaching agent needs to be controlled within the range of the invention, the excessive pH value can cause the compound of amphoteric metal elements such as aluminum and the like to be dissolved under the strong alkaline condition, and the excessive pH value can not completely remove impurity elements such as magnesium, manganese and the like.
In the method, the content of lithium oxide in the lithium salt solution is preferably 15-20 g/L.
In the above method, preferably, the mechanical activation treatment is a process of grinding the lepidolite to an average particle size of less than 20 μm by using a ball mill, a Raymond mill and/or a micro-powder mill. According to the method, lepidolite is subjected to mechanical activation treatment, so that mica is peeled and separated from feldspar, quartz and the like, the surface area is increased by crushing, the activation energy is reduced by mechanical activation, and the temperature of a boiling reconstitution reaction is favorably reduced.
The technical scheme of the invention mainly relates to the following chemical reaction equation:
lepidolite has the chemical formula K (Li, Al)2.5-3[Si3.5-3Al0.5-1O10](OH,F)2It can be abbreviated as: MeF MeOH Al2O3·3SiO2(ii) a Wherein Me is Li, Na, K, Rb, Cs;
(a) low-temperature chemical activation stage:
MeF·MeOH·Al2O3·3SiO2+4H2SO4→Me2SO4+Al2(SO4)3+HF↑+3SiO2+4H2O；
MeF·MeOH·Al2O3·3SiO2+8HCl→2MeCl+2AlCl3+HF↑+3SiO2+4H2O；
MeF·MeOH·Al2O3·3SiO2+7HF→2MeF+2AlF3+3SiO2+4H2O；
MeF·MeOH·Al2O3·3SiO2+8HNO3→2MeNO3+2Al(NO3)3+HF↑+3SiO2+4H2O；
MO+H2SO4→H2O+MSO4(M is Fe, Cu, Mn, Mg, Ca), and the reaction equation of the divalent metal element and other inorganic acids is as described above.
(b) The intermediate-temperature roasting reduction stage is considered as a complex salt, so that the sodium salt is taken as an example, and the chemical reaction formula is as follows:
2[MeF·MeOH·Al2O3·3SiO2]+2Na2SO4→2Me2SO4+3NaAlSi2O6+NaAlF2(OH)2；
2[MeF·MeOH·Al2O3·3SiO2]+4NaCl→4MeCl+3NaAlSi2O6+NaAlF2(OH)2；
2[MeF·MeOH·Al2O3·3SiO2]+4NaNO3→4MeNO3+3NaAlSi2O6+NaAlF2(OH)2；
2[MeF·MeOH·Al2O3·3SiO2]+4NaF→4MeF+3NaAlSi2O6+NaAlF2(OH)2；
Al2(SO4)3·18H2O→Al2O3+3SO3+18H2o (medium temperature decomposition);
2AlCl3·6H2O→Al2O3+6HCl+3H2o (medium temperature decomposition);
since the inorganic acid and the reconstruction agent are of various types, the reaction chemical equation is only illustrated and not listed.
(c) The leaching stage involves the following chemical equation:
Me2SO4+Al2(SO4)3→2MeAl(SO4)2(Me is Na, K, Rb, Cs, NH4 +)；
The primary leaching impurity removal process relates to a chemical equation, and takes chloride and sulfate impurities as an example, and adopts a sodium hydroxide gradual leaching agent for leaching:
MCl2+2NaOH→M(OH)2+2NaCl；
MSO4+2NaOH→M(OH)2+Na2SO4。
compared with the prior art, the invention has the advantages that:
the method adopts two-step activation, and combines mechanical activation and chemical activation, wherein the mechanical activation is firstly adopted to reduce the particle size of the material, increase the specific surface area and reduce the reaction activation energy, and then the chemical activation is combined to carry out low-temperature and simple acidification treatment to destroy the compact protective film on the mica surface, so that the reconstruction agent can enter the sheet structure of the mica layer in the boiling reconstruction process to rapidly generate ion exchange reaction.
The method of the invention improves the extraction rate of valuable metal elements in lepidolite and the comprehensive value of waste residue after extracting alkali metals such as lithium and the like, reduces the temperature and time of reconstruction reaction, realizes the recycling of reconstruction agent raw materials, and realizes the high-efficiency dissolution of alkali metal salts and the synchronous separation of impurities such as iron, aluminum, manganese and the like.
The invention takes the technology of processing lepidolite by an ore phase reconstruction method to extract battery-grade lithium carbonate as the background, fully utilizes potassium, sodium, aluminum elements and fluorine elements in the lepidolite to generate cryolite which is insoluble in acid as a fluxing agent, utilizes sodium and potassium salts in the lepidolite and a system as reconstruction agents, does not need to additionally add raw materials such as potassium, sodium, aluminum and the like in the whole process, has the characteristics of short flow, low reconstruction temperature and low energy consumption compared with the process of mineral phase reconstruction by calcium chloride, and simultaneously accurately controls the production processes, the proportion of each procedure and the reaction time, and has high recovery rate of alkali metal. All the steps are mutually cooperated, so that economical and efficient utilization of the lepidolite is realized together, and large-scale development and utilization of the lepidolite resource are facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart of the process for extracting alkali metal by treating lepidolite in example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In each example, tantalum-niobium lithium ore produced in Yichun Jiangxi was selected, and the main components of lepidolite are shown in Table 1.
TABLE 1 lepidolite mineral composition
| K | Na | Rb | Cs | Fe | Mn | Li2O | CaO | F | SiO2 | Al2O3 | |
| Wt/％ | 6.45 | 1.25 | 1 | 0.2 | 0.13 | 0.24 | 4.2 | 0.14 | 4.46 | 50.78 | 26.93 |
Example 1:
the invention relates to a method for extracting alkali metal by treating lepidolite, which comprises the following steps:
according to the process flow shown in figure 1, firstly, a ball mill is adopted to grind lepidolite to the average particle size of less than 20 mu m, the mechanically activated lepidolite is uniformly mixed with a reconstruction agent (formed by mixing sodium sulfate and potassium sulfate according to the mass ratio of 1: 1) to obtain a mixture, the mass ratio of the lepidolite to the reconstruction agent is 2:1, then the mixture and 50% sulfuric acid are uniformly mixed, the mass ratio of the sulfuric acid to the mixture is 1:1, and the mixture is reacted for 2 hours at 80 ℃; then heating to 700 ℃, reacting for 60s, and cooling to 150 ℃ to obtain reconstructed clinker; and finally, adding the reconstructed clinker into an alkaline calcium hydroxide solution with the pH value of 12, leaching alkali metal ions, and synchronously removing impurities through solid-liquid separation to obtain a lithium salt solution rich in alkali metal and solid impurities. The lithium salt solution has lithium oxide content up to 17g/L, low content of aluminum, iron, nickel, cobalt, manganese and fluorine ions, and solid impurities mainly comprise sodium aluminosilicate, potassium aluminosilicate, a small amount of calcium sulfate and calcium fluoride.
The dissolution yield of alkali metals in the lepidolite concentrate after boiling reconstitution is respectively as follows: li 93.18%, K94.25%, Rb92.01%, Cs 91.15%.
The content of lithium oxide in the obtained lithium salt solution reaches 17g/L, the content of other impurities is low, and specific detection results are shown in Table 2.
Table 2 composition of lithium salt solution in example 1
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 17.01 | 10.13 | 12.75 | 1.65 | 0.14 | 0.05 | 0.33 | 0.01 | 0.01 | 0.01 | -- |
Example 2:
the invention relates to a method for extracting alkali metal by treating lepidolite, which comprises the following steps:
grinding lepidolite to an average particle size of less than 20 mu m by adopting combined treatment of a Raymond mill and a ball mill, uniformly mixing the mechanically activated lepidolite with a reconstruction agent (formed by mixing sodium sulfate and potassium sulfate according to a mass ratio of 1: 1) to obtain a mixture, wherein the mass ratio of the lepidolite to the reconstruction agent is 2.5:1, uniformly mixing the mixture and 50% of sulfuric acid by mass fraction, and reacting for 3 hours at 60 ℃, wherein the mass ratio of the sulfuric acid to the mixture is 1.5: 1; then heating to 800 ℃, reacting for 30s, and cooling to 200 ℃ to obtain reconstructed clinker; and finally, adding the reconstructed clinker into an alkaline calcium hydroxide solution with the pH value of 12, leaching alkali metal ions, and synchronously removing impurities through solid-liquid separation to obtain a lithium salt solution rich in alkali metal and solid impurities. The lithium salt solution has lithium oxide content up to 15.65g/L, low content of aluminum, iron, nickel, cobalt, manganese and fluorine ions, and solid impurities mainly comprise sodium aluminosilicate, potassium aluminosilicate, a small amount of calcium sulfate and calcium fluoride.
The dissolution yield of alkali metals in the lepidolite concentrate after boiling reconstitution is respectively as follows: li 95.72%, K95.04%, Rb93.11%, Cs 91.88%.
The content of lithium oxide in the obtained lithium salt solution reaches 15.65g/L, the content of other impurities is low, and specific detection results are shown in Table 3.
Table 3 composition of lithium salt solution in example 2
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 15.65 | 9.43 | 10.17 | 1.22 | 0.13 | 0.02 | 0.29 | -- | 0.01 | 0.01 | -- |
Example 3:
the invention relates to a method for extracting alkali metal by treating lepidolite, which comprises the following steps:
grinding lepidolite to an average particle size of less than 20 microns by using a micro powder mill, uniformly mixing the mechanically activated lepidolite with a reconstruction agent (formed by mixing sodium sulfate and potassium sulfate according to a mass ratio of 1: 1) to obtain a mixture, wherein the mass ratio of the lepidolite to the reconstruction agent is 3:1, uniformly mixing the mixture with 50% by mass of sulfuric acid, and reacting for 4 hours at 100 ℃, wherein the mass ratio of the sulfuric acid to the mixture is 2: 1; then heating to 750 ℃, reacting for 40s, and cooling to 250 ℃ to obtain reconstructed clinker; and finally, adding the reconstructed clinker into an alkaline calcium hydroxide solution with the pH value of 12, leaching alkali metal ions, and synchronously removing impurities through solid-liquid separation to obtain a lithium salt solution rich in alkali metal and solid impurities. The lithium salt solution has lithium oxide content up to 18.52g/L, low aluminum, iron, nickel, cobalt, manganese and fluorine ion content, and solid impurities mainly comprise sodium aluminosilicate, potassium aluminosilicate, a small amount of calcium sulfate and calcium fluoride.
The dissolution yield of alkali metals in the lepidolite concentrate after boiling reconstitution is respectively as follows: li 94.55%, K93.82%, Rb91.93% and Cs 91.00%.
The content of lithium oxide in the obtained lithium salt solution reaches 18.52g/L, the content of other impurities is low, and specific detection results are shown in Table 4.
Table 4 composition of lithium salt solution in example 3
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 18.52 | 11.21 | 14.06 | 1.75 | 0.19 | 0.06 | 0.37 | 0.02 | 0.02 | 0.02 | -- |
Example 4:
the invention relates to a method for extracting alkali metal by treating lepidolite, which comprises the following steps:
grinding lepidolite to an average particle size of less than 20 microns by adopting combined treatment of a Raymond mill and a micropowder mill, uniformly mixing the mechanically activated lepidolite with a reconstruction agent (formed by mixing sodium chloride and potassium chloride according to a mass ratio of 1: 1) to obtain a mixture, wherein the mass ratio of the lepidolite to the reconstruction agent is 5:1, uniformly mixing the mixture with 33% hydrochloric acid by mass, wherein the mass ratio of the hydrochloric acid to the mixture is 1:1, and reacting for 2 hours at 60 ℃; then heating to 550 ℃, reacting for 60s, and cooling to 180 ℃ to obtain reconstructed clinker; and finally, adding the reconstructed clinker into an alkaline calcium hydroxide solution with the pH value of 12, leaching alkali metal ions, and synchronously removing impurities through solid-liquid separation to obtain a lithium salt solution rich in alkali metal and solid impurities. The lithium salt solution has lithium oxide content up to 10.78g/L, low Al, Fe, Ni, Co, Mn and F ion content, and solid impurity mainly including sodium aluminosilicate, potassium aluminosilicate, small amount of calcium sulfate and calcium fluoride.
The dissolution yield of alkali metals in the lepidolite concentrate after boiling reconstitution is respectively as follows: li 90.52%, K89.78%, Rb87.51%, Cs 87.17%.
The content of lithium oxide in the obtained lithium salt solution reaches 10.78g/L, the content of other impurities is low, and specific detection results are shown in Table 5.
Table 5 composition of lithium salt solution in example 4
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 10.78 | 7.52 | 9.16 | 1.03 | 0.11 | 0.07 | 0.21 | 0.98 | 0.01 | 0.01 | -- |
Example 5:
the invention relates to a method for extracting alkali metal by treating lepidolite, which comprises the following steps:
grinding lepidolite to an average particle size of less than 20 microns by adopting combined treatment of a Raymond mill and a micronizing mill, uniformly mixing the mechanically activated lepidolite with a reconstruction agent (formed by mixing sodium chloride and potassium chloride according to a mass ratio of 1: 1) to obtain a mixture, wherein the mass ratio of the lepidolite to the reconstruction agent is 4:1, uniformly mixing the mixture with an acidic activating agent, wherein the acidic activating agent is specifically 33% hydrochloric acid and 40% hydrofluoric acid, and the mass ratio of the hydrochloric acid to the hydrofluoric acid to the mixture is 1:0.5:1, and reacting for 4 hours at 60 ℃; then heating to 750 ℃, reacting for 45s, and cooling to 200 ℃ to obtain reconstructed clinker; and finally, adding the reconstructed clinker into an alkaline calcium hydroxide solution with the pH value of 12, leaching alkali metal ions, and synchronously removing impurities through solid-liquid separation to obtain a lithium salt solution rich in alkali metal and solid impurities. The lithium salt solution has lithium oxide content up to 12.55g/L, low content of aluminum, iron, nickel, cobalt, manganese and fluorine ions, and solid impurities mainly comprise sodium aluminosilicate, potassium aluminosilicate, a small amount of calcium sulfate and calcium fluoride.
The dissolution yield of alkali metals in the lepidolite concentrate after boiling reconstitution is respectively as follows: li 91.19%, K91.07%, Rb89.58% and Cs 88.72%.
The content of lithium oxide in the obtained lithium salt solution reaches 12.55g/L, the content of other impurities is low, and specific detection results are shown in Table 6.
Table 6 composition of lithium salt solution in example 5
| Li2O | K | Na | Rb | Cs | Fe | Mn | Al | Ni | Co | F | |
| g/L | 12.55 | 9.78 | 11.77 | 1.28 | 0.16 | 0.01 | 0.28 | 0.07 | 0.01 | 0.01 | -- |
Claims (5)
1. A method for processing lepidolite to extract alkali metal is characterized by comprising the following steps:
uniformly mixing the mechanically activated lepidolite with a reconstruction agent to obtain a mixture, uniformly mixing the mixture with an acidic activating agent, and reacting for 1-4 hours at 50-100 ℃; then heating to 500-800 ℃, reacting for 10-60 s, and cooling to 150-250 ℃ to obtain reconstructed clinker; finally, adding the reconstructed clinker into an alkaline leaching agent, leaching alkali metal ions, and synchronously removing impurities through solid-liquid separation to obtain a lithium salt solution rich in alkali metal and solid impurities;
the reconstruction agent is sulfate and/or chloride of sodium and potassium; the acidic activating agent is sulfuric acid, hydrochloric acid, nitric acid and/or hydrofluoric acid;
the alkaline leaching agent is a calcium hydroxide and/or sodium hydroxide solution, and the pH value of the alkaline leaching agent is 10-12.
2. The method according to claim 1, wherein the mass ratio of the lepidolite to the restructuring agent is (2-5): 1.
3. The method according to claim 1, wherein the mass ratio of the acidic activator to the mixture is (1-3): 1.
4. The method of claim 1, wherein the lithium salt solution contains 15 to 20g/L of lithium oxide.
5. The method according to claim 1, wherein the mechanical activation treatment is milling of the lepidolite to an average particle size of less than 20 μm using a ball mill, a Raymond mill and/or a micronizing mill.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711243215.6A CN107964597B (en) | 2017-11-30 | 2017-11-30 | Method for extracting alkali metal by treating lepidolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711243215.6A CN107964597B (en) | 2017-11-30 | 2017-11-30 | Method for extracting alkali metal by treating lepidolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107964597A CN107964597A (en) | 2018-04-27 |
| CN107964597B true CN107964597B (en) | 2020-05-29 |
Family
ID=61999208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711243215.6A Active CN107964597B (en) | 2017-11-30 | 2017-11-30 | Method for extracting alkali metal by treating lepidolite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107964597B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482576B (en) * | 2019-09-26 | 2022-05-06 | 福州大学 | Method for preparing lithium salt from lepidolite through hydrothermal method |
| CN111534705A (en) * | 2020-04-21 | 2020-08-14 | 华南理工大学 | Composite additive for treating lepidolite ore and application thereof |
| CN114737066B (en) * | 2022-04-20 | 2024-01-12 | 北京中科云腾科技有限公司 | Method for extracting lithium from leaching residues of lithium ores |
| CN114875250B (en) * | 2022-05-18 | 2023-08-01 | 北京机械力化学研究院有限公司 | Method for purifying lithium from lithium-containing clay |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101989A (en) * | 1985-04-01 | 1986-09-17 | 广州有色金属研究院 | Processing method with preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 |
| CN105803188A (en) * | 2016-05-30 | 2016-07-27 | 江西旭锂矿业有限公司 | Method for preferential segregation of potassium, rubidium and cesium through chloridizing roasting treatment of lepidolite |
| CN106222450A (en) * | 2016-07-21 | 2016-12-14 | 温岭市亿林投资有限公司 | Lithium, rubidium and the extracting method of caesium in a kind of zinnwaldite ore deposit |
| CN107267754A (en) * | 2017-06-01 | 2017-10-20 | 江西南氏锂电新材料有限公司 | A kind of method that utilization sulfuric acid extracts alkali metal salt with lepidolite low-temperature solid phase reaction |
| WO2017200408A1 (en) * | 2016-05-18 | 2017-11-23 | Instituto Superior Técnico | Process of lithium extraction from ores and concentrates by mechanical activation and reaction with sulphuric acid |
-
2017
- 2017-11-30 CN CN201711243215.6A patent/CN107964597B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85101989A (en) * | 1985-04-01 | 1986-09-17 | 广州有色金属研究院 | Processing method with preparation of Li 2 CO 3 by treating lithium-loaded mica with K 2 SO 4 |
| WO2017200408A1 (en) * | 2016-05-18 | 2017-11-23 | Instituto Superior Técnico | Process of lithium extraction from ores and concentrates by mechanical activation and reaction with sulphuric acid |
| CN105803188A (en) * | 2016-05-30 | 2016-07-27 | 江西旭锂矿业有限公司 | Method for preferential segregation of potassium, rubidium and cesium through chloridizing roasting treatment of lepidolite |
| CN106222450A (en) * | 2016-07-21 | 2016-12-14 | 温岭市亿林投资有限公司 | Lithium, rubidium and the extracting method of caesium in a kind of zinnwaldite ore deposit |
| CN107267754A (en) * | 2017-06-01 | 2017-10-20 | 江西南氏锂电新材料有限公司 | A kind of method that utilization sulfuric acid extracts alkali metal salt with lepidolite low-temperature solid phase reaction |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107964597A (en) | 2018-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107964597B (en) | Method for extracting alkali metal by treating lepidolite | |
| KR101682217B1 (en) | A Method Of Manufacturing A Lithium Carbonate With High Purity By Recycling A Lithium From A Anode Material Of Used Lithium Ion Secondary Battery | |
| CN103145158B (en) | Method for preparing lithium carbonate from lepidolite through sulfuric acid roasting method | |
| CN102718234B (en) | Method for extracting lithium carbonate from lepidolite | |
| KR102278372B1 (en) | Method for recoering lithium from lithium compound | |
| CN110550644B (en) | Method for separating and extracting battery-grade lithium carbonate, rubidium and cesium salts from lepidolite | |
| CN102020294B (en) | Lithium hydroxide monohydrate and preparation method thereof | |
| CN105039699B (en) | The solid fluorine reconstruct extraction alkali metal Slag treatment of lepidolite and resource utilization method | |
| CN109336140B (en) | Process for extracting lithium by adding lithium iron phosphate into lepidolite | |
| CN108004391B (en) | A method of processing lepidolite extracts metallic element | |
| CN103789553B (en) | Method for comprehensively utilizing lepidolite mineralogical reconstruction lithium-extraction slags | |
| CN101974678A (en) | Method for extracting lithium and other alkali metal elements from lepidolite mineral | |
| CN108330298B (en) | Method for extracting rubidium, cesium, lithium and potassium from polymetallic mica ore | |
| CN115216645B (en) | Method for extracting lithium from electrolytic aluminum waste residue by mixed salt calcination | |
| CN101885496A (en) | Process for extracting lithium from lithionite by fluorine chemistry | |
| CN104140117A (en) | Process for extracting lithium salt by adopting method for autoclaving lepidolite with sulfuric acid | |
| WO2023226546A1 (en) | Method for recycling lithium from lithium clay | |
| CN111534705A (en) | Composite additive for treating lepidolite ore and application thereof | |
| CN108281726B (en) | Method for extracting lithium hydroxide from lithium phosphate-containing waste residues | |
| CN113651342A (en) | Method for producing lithium product by processing lepidolite through nitric acid atmospheric pressure method | |
| CN108118143B (en) | Method for preparing lithium carbonate by extracting lithium from lepidolite through two-stage chlorination roasting-alkali liquor leaching method | |
| CN109022772A (en) | A kind of method that lepidolite ore is leached in sulfuric acid curing | |
| CN102417995A (en) | Process for extracting lithium from lithium pyroxene concentrate by using fluorine chemistry | |
| CN108516569B (en) | Method for preparing lithium sulfate solution by roasting lepidolite | |
| CN108063295B (en) | Method for extracting lithium from slag generated by pyrogenic recovery of lithium battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220615 Address after: 410000 Room 502, building 16, gaojiaping, Yuelu District, Changsha City, Hunan Province Patentee after: Li Jiayi Address before: 410000 room 1301, building 1, Yanggu Jinyuan, No. 39, Luhu Road, Changsha hi tech Development Zone, Changsha City, Hunan Province Patentee before: HUNAN ZHONGDA TECHNOLOGY ESTABLISH A BUSINESS INCUBATOR CO.,LTD. |