CN114752784B - Technology for improving lithium leaching rate in lepidolite - Google Patents
Technology for improving lithium leaching rate in lepidolite Download PDFInfo
- Publication number
- CN114752784B CN114752784B CN202210212875.2A CN202210212875A CN114752784B CN 114752784 B CN114752784 B CN 114752784B CN 202210212875 A CN202210212875 A CN 202210212875A CN 114752784 B CN114752784 B CN 114752784B
- Authority
- CN
- China
- Prior art keywords
- lithium
- lepidolite
- leaching
- energy ball
- ball milling
- 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
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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a process for improving the leaching rate of lithium in lepidolite; according to the invention, lepidolite ore powder is added with an activating agent and a pore-forming agent for high-energy ball milling; presintering the obtained composite material; roasting and defluorinating the pre-sintered clinker; mixing the roasted defluorinated clinker with leaching auxiliary materials, and carrying out pressure cooking reaction; separating the mother liquor obtained by pressure boiling from slag, adding active carbon and caustic soda into the mother liquor, stirring, filtering, and collecting filtrate; introducing CO into the filtrate 2 Carbonizing and precipitating lithium; filtering, collecting filter residues, and washing to obtain crude lithium carbonate. The invention adopts a high-energy ball milling activation process to ensure that the lepidolite crude ore with smooth and compact structure becomes loose and porous, and simultaneously damages the original stable structure to realize the high-efficiency removal of fluorine and the high-efficiency leaching of lithium. The lithium extraction process provided by the invention is simple and efficient, has low cost, effectively solves the problems of difficult defluorination and low lithium collection rate of the lepidolite ore, and realizes the full utilization of the lepidolite ore.
Description
Technical Field
The invention belongs to the technical field of ore extraction, and particularly relates to a process for improving the leaching rate of lithium in lepidolite.
Background
With the increasing popularity of digital electronic products and the rapid development of new energy automobile industry, lithium resources have become a very important strategic resource. The lithium resource is generally extracted through salt lake brine and lithium ore, wherein the cost of the salt lake lithium extraction technology is low, and the development is very mature. But the common position of the salt lake in China is far away, the altitude is high, and the exploitation difficulty is high. Meanwhile, the magnesium-lithium ratio is high, and the separation is difficult. Therefore, the lithium resource in the current stage of China mainly depends on the extraction of lithium from ores. However, the exploitation and selection technology of lithium ores in China is relatively backward, and in addition, the lithium ores have the problems of low grade, unstable quality, high exploitation cost and the like. Lithium extraction is therefore currently mainly carried out by imported spodumene. In order to get rid of the dependence on the import of the lithium ore as soon as possible, it is urgent to develop how to efficiently extract lithium from the domestic lithium mica ore with abundant reserves. Lepidolite has complex components and is tightly combined with elements such as silicon, aluminum, fluorine and the like, so that the extraction rate of lithium is low. The main current technology adopted at present is mainly to crush lepidolite and defluorinate water vapor to destroy the stable structure of lepidolite ore, thereby being more beneficial to the dissolution of lithium. The process described in patent CN202010154975.5 "a method for preparing lithium carbonate from lepidolite powder". However, since the crushing and grain refining of lepidolite ore requires high economic and time costs and is limited by the crushing and pulverizing process, the ore cannot be pulverized into an ideal particle size industrially, which also causes incomplete utilization of the ore.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a process for improving the leaching rate of lithium in lepidolite. The invention innovatively provides a high-energy mechanical activation process in the lithium extraction process of lepidolite, and the crushed lepidolite is subjected to secondary treatment by adding an activating agent and a pore-forming agent. In the high-energy mechanical activation, the activator fully enters the inside of the lepidolite ore to destroy the original stable chemical structure of the lepidolite ore, and the pore-forming agent can manufacture holes in the inside of the ore particles. By this treatment process, lepidolite particles with higher chemical activity and looser structure are obtained. Therefore, in the subsequent defluorination roasting process, fluorine in the ore can be more fully reacted with high-temperature steam to obtain lepidolite concentrate with higher defluorination degree. And then, through a series of leaching, separating, removing impurities, precipitating lithium and washing processes, the lithium carbonate is finally obtained, and the high-efficiency lithium extraction with the extraction rate up to 88% is realized.
The aim of the invention is achieved by the following technical scheme:
a process for improving the leaching rate of lithium in lepidolite comprises the following steps:
(1) High-energy ball milling activation: adding an activating agent and a pore-forming agent into lepidolite ore powder for high-energy ball milling;
(2) Presintering: presintering the composite material activated by high-energy ball milling in the step (1);
(3) Roasting and defluorination: introducing water vapor into the clinker pre-sintered in the step (2), and roasting and defluorinating the clinker;
(4) And (3) pressure cooking: mixing the roasted defluorinated clinker in the step (3) with leaching auxiliary materials, and carrying out pressure cooking reaction; dissolving out alkali metal in clinker;
(5) Separating and purifying: separating the mother liquor obtained in the step (4) from slag, adding active carbon and caustic soda into the mother liquor, stirring, filtering and collecting filtrate;
(6) Carbonizing and precipitating lithium: introducing CO into the filtrate separated and purified in the step (5) 2 Carbonizing and precipitating lithium until the PH value of the filtrate reaches 11-12;
(7) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium in the step (6), collecting filter residues, and washing to obtain crude lithium carbonate.
Preferably, the particle size of the lepidolite ore powder in the step (1) is 100-300 meshes; the lepidolite ore powder is obtained by crushing and pulverizing lepidolite; the apparatus for crushing and pulverizing comprises one or more of the following: jaw crusher, twin roll mill, cone crusher, sand making machine, hammer crusher, planetary ball mill, high energy ball mill, rotary drum ball mill.
Preferably, the activating agent in the step (1) is one or more of oxalic acid, boric acid, phosphoric acid, monoammonium phosphate, hydrogen peroxide, sodium hydroxide, potassium hydroxide, hydrazine hydrate and potassium permanganate; the pore-forming agent is one or more of ammonium carbonate, ammonium chloride, ammonium nitrate, sodium carbonate, sodium bicarbonate, potassium carbonate, polymethyl methacrylate and polyoxyethylene polyoxypropylene ether block copolymer.
Preferably, the mass ratio of the activator to the lepidolite ore powder in the step (1) is 0.02-0.08: 1, a step of;
preferably, the mass ratio of the pore-forming agent to the lepidolite ore powder in the step (1) is 0.01-0.05: 1, a step of;
preferably, the high-energy ball milling in the step (1) is performed by using a high-energy ball mill; the rotating speed of the high-energy ball milling is 700-1200 r/min, and the time is 1-6 h.
Preferably, the temperature of the presintering in the step (2) is 200-600 ℃ and the time is 30min-4h.
Preferably, the steam in the step (3) is introduced into the clinker in an amount of 0.01m per ton of clinker 3 /h-0.5m 3 /h; the roasting defluorination temperature is 400-1000 ℃ and the time is 30min-4h.
Preferably, the leaching auxiliary material in the step (4) is a mixture of a leaching agent and a precipitating agent.
Further preferably, the leaching agent comprises one or more of sodium chloride, ferric chloride, cupric chloride, manganese chloride, nickel chloride, calcium chloride, zinc chloride, sodium sulfate, ferric sulfate, cupric sulfate, manganese sulfate, nickel sulfate, and zinc sulfate;
further preferably, the precipitant comprises one or more of calcium oxide, calcium hydroxide, and quicklime.
Preferably, the temperature of the autoclaving reaction in the step (4) is 120-300 ℃ and the time is 2-12h.
Preferably, the mass ratio of the caustic soda to the lithium in the mother liquor in the step (5) is 1.1-1.5:1, a step of; the mass ratio of the active carbon to lithium in the mother solution is 0.02-0.1:1.
compared with the prior art, the invention has the following advantages:
the invention adopts a simple mechanical activation process to carry out secondary treatment on the crushed lepidolite ore, adopts a method of combining a surface activator and a pore-forming agent, damages the original compact structure and stable chemical phase of the lepidolite ore in the high-energy ball milling activation process, is beneficial to the full extraction of fluorine in the subsequent defluorination roasting process and the full extraction of lithium in the pressure cooking process, and effectively improves the extraction rate of lithium. The invention has simple process flow, low energy consumption, obvious effect and wide market prospect.
Detailed Description
The present invention will be specifically described with reference to the following examples, but the embodiments and the scope of the present invention are not limited to the following examples.
The invention takes Jiangxi Yichun lepidolite ore as raw material, and the main chemical components and proportions are shown in the following table 1:
TABLE 1
In order to show the advantages of more thorough defluorination and higher lithium leaching rate by the combination of high-energy ball milling activation and defluorination roasting, the high-energy ball milling activation is not performed in example 1, the roasting defluorination is not performed in example 2, only the activator is added in example 3, and only the pore-forming agent is added in example 4. While examples 5-7 performed all steps.
Example 1
The lepidolite crude ore is put into a jaw crusher for crushing, then ball-milled for 6 hours, and sieved, and ore powder with the granularity of 200 meshes is selected.
(1) High-temperature pretreatment: the ore powder was subjected to presintered at 400 ℃ for 30min.
(2) Roasting and defluorination: the pretreated clinker is put into a reaction furnace, and the flow rate is 0.01m 3 Steam/h, roasting temperature is 500 ℃, and defluorination time is 30min. The fluorine content after defluorination is shown in table 3.
(3) And (3) pressure cooking: the defluorinated clinker, sodium chloride and quicklime are put into a high-pressure reaction kettle together, and are boiled under pressure for 4 hours at 150 ℃ to fully dissolve out lithium.
(4) Separating and purifying: separating the mother liquor obtained by pressure boiling from slag, adding active carbon and caustic soda (the mass ratio of the caustic soda to lithium in the mother liquor is 1.1:1), fully stirring, filtering again, and collecting filtrate.
(5) Carbonizing and precipitating lithium: introducing CO into the purified filtrate 2 And (5) carbonizing and precipitating lithium until the pH value of the filtrate reaches 11.
(6) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium, collecting filter residues, and repeatedly washing to obtain crude lithium carbonate.
The leaching rate of lithium in this example was analyzed by the quality of the lithium carbonate obtained, and the results are shown in Table 2.
Example 2
The lepidolite crude ore is put into a jaw crusher for crushing, then ball-milled for 6 hours, and sieved, and ore powder with the granularity of 200 meshes is selected.
(1) High energy mechanical activation: the lepidolite ore powder is put into a high-energy ball mill, and an activator oxalic acid (the mass ratio of the activator oxalic acid to the lepidolite is (0.02:1), a pore-forming agent ammonium carbonate (the mass ratio of the lepidolite is (0.01:1)) is added for high-energy ball milling, the rotating speed is set to 800r/min, and the ball milling time is 2 hours.
(2) High-temperature pretreatment: the composites subjected to high energy mechanical activation were pre-sintered at 400 ℃ for 30min.
(3) And (3) pressure cooking: the pretreated clinker is put into a high-pressure reaction kettle together with sodium chloride and quicklime, and is boiled under pressure for 4 hours at 150 ℃ to fully dissolve out lithium.
(4) Separating and purifying: separating the mother liquor obtained by pressure boiling from slag, adding active carbon and caustic soda (the mass ratio of the caustic soda to lithium in the mother liquor is 1.1:1), fully stirring, filtering again, and collecting filtrate.
(5) Carbonizing and precipitating lithium: introducing CO into the purified filtrate 2 And (5) carbonizing and precipitating lithium until the pH value of the filtrate reaches 11.
(6) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium, collecting filter residues, and repeatedly washing to obtain crude lithium carbonate.
The leaching rate of lithium in this example was analyzed by the quality of the lithium carbonate obtained, and the results are shown in Table 2.
Example 3
The lepidolite crude ore is put into a jaw crusher for crushing, then ball-milled for 6 hours, and sieved, and ore powder with the granularity of 200 meshes is selected.
(1) High energy mechanical activation: the lepidolite ore powder is put into a high-energy ball mill, and activator oxalic acid (the mass ratio of the lepidolite to the lepidolite is 0.02:1) is added for high-energy ball milling, the rotating speed is set to 800r/min, and the ball milling time is 2 hours.
(2) High-temperature pretreatment: the composites subjected to high energy mechanical activation were pre-sintered at 400 ℃ for 30min.
(3) Roasting and defluorination: the pretreated clinker is put into a reaction furnace, and the flow rate is 0.01m 3 Steam/h, roasting temperature is 500 ℃, and defluorination time is 30min. The fluorine content after defluorination is shown in table 3.
(4) And (3) pressure cooking: the defluorinated clinker, sodium chloride and quicklime are put into a high-pressure reaction kettle together, and are boiled under pressure for 4 hours at 150 ℃ to fully dissolve out lithium.
(5) Separating and purifying: separating the mother liquor obtained by pressure boiling from slag, adding active carbon and caustic soda (the mass ratio of the caustic soda to lithium in the mother liquor is 1.1:1), fully stirring, filtering again, and collecting filtrate.
(6) Carbonizing and precipitating lithium: introducing CO into the purified filtrate 2 And (5) carbonizing and precipitating lithium until the pH value of the filtrate reaches 11.
(7) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium, collecting filter residues, and repeatedly washing to obtain crude lithium carbonate.
The leaching rate of lithium in this example was analyzed by the quality of the lithium carbonate obtained, and the results are shown in Table 2.
Example 4
The lepidolite crude ore is put into a jaw crusher for crushing, then ball-milled for 6 hours, and sieved, and ore powder with the granularity of 200 meshes is selected.
(1) High energy mechanical activation: the lepidolite ore powder is put into a high-energy ball mill, and a pore-forming agent ammonium carbonate (the mass ratio of lepidolite is (0.01:1)) is added for high-energy ball milling, the rotating speed is set to 800r/min, and the ball milling time is 2 hours.
(2) High-temperature pretreatment: the composites subjected to high energy mechanical activation were pre-sintered at 400 ℃ for 30min.
(3) Roasting and defluorination: the pretreated clinker is put into a reaction furnace, and the flow rate is 0.01m 3 Steam/h, roasting temperature is 500 ℃, and defluorination time is 30min. The fluorine content after defluorination is shown in table 3.
(4) And (3) pressure cooking: the defluorinated clinker, sodium chloride and quicklime are put into a high-pressure reaction kettle together, and are boiled under pressure for 4 hours at 150 ℃ to fully dissolve out lithium.
(5) Separating and purifying: separating the mother liquor obtained by pressure boiling from slag, adding active carbon and caustic soda (the mass ratio of the caustic soda to lithium in the mother liquor is 1.1:1), fully stirring, filtering again, and collecting filtrate.
(6) Carbonizing and precipitating lithium: introducing CO into the purified filtrate 2 And (5) carbonizing and precipitating lithium until the pH value of the filtrate reaches 11.
(7) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium, collecting filter residues, and repeatedly washing to obtain crude lithium carbonate.
The leaching rate of lithium in this example was analyzed by the quality of the lithium carbonate obtained, and the results are shown in Table 2.
Example 5
The lepidolite crude ore is put into a jaw crusher for crushing, then ball-milled for 6 hours, and sieved, and ore powder with the granularity of 200 meshes is selected.
(1) High energy mechanical activation: the lepidolite ore powder is put into a high-energy ball mill, and an activator oxalic acid (the mass ratio of the activator oxalic acid to the lepidolite is (0.02:1), a pore-forming agent ammonium carbonate (the mass ratio of the lepidolite is (0.01:1)) is added for high-energy ball milling, the rotating speed is set to 800r/min, and the ball milling time is 2 hours.
(2) High-temperature pretreatment: the composites subjected to high energy mechanical activation were pre-sintered at 400 ℃ for 30min.
(3) Roasting and defluorination: the pretreated clinker is put into a reaction furnace, and the flow rate is 0.01m 3 Steam/h, roasting temperature is 500 ℃, and defluorination time is 30min. The fluorine content after defluorination is shown in table 3.
(4) And (3) pressure cooking: the defluorinated clinker, sodium chloride and quicklime are put into a high-pressure reaction kettle together, and are boiled under pressure for 4 hours at 150 ℃ to fully dissolve out lithium.
(5) Separating and purifying: separating the mother liquor obtained by pressure boiling from slag, adding active carbon and caustic soda (the mass ratio of the caustic soda to lithium in the mother liquor is 1.1:1), fully stirring, filtering again, and collecting filtrate.
(6) Carbonizing and precipitating lithium: introducing CO into the purified filtrate 2 And (5) carbonizing and precipitating lithium until the pH value of the filtrate reaches 11.
(7) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium, collecting filter residues, and repeatedly washing to obtain crude lithium carbonate.
The leaching rate of lithium in this example was analyzed by the quality of the lithium carbonate obtained, and the results are shown in Table 2.
Example 6
The lepidolite crude ore is put into a jaw crusher for crushing, then ball-milled for 6 hours, and sieved, and ore powder with the granularity of 200 meshes is selected.
(1) High energy mechanical activation: the lepidolite ore powder is put into a high-energy ball mill, and activator oxalic acid (the mass ratio of the activator oxalic acid to the lepidolite is 0.03:1) is added, and the ammonium carbonate serving as a pore-forming agent (the mass ratio of the ammonium carbonate to the lepidolite is 0.02:1) is subjected to high-energy ball milling, wherein the rotating speed is set to 1000r/min, and the ball milling time is 4 hours.
(2) High-temperature pretreatment: the composites subjected to high energy mechanical activation were pre-sintered at 500 ℃ for 2h.
(3) Roasting and defluorination: the pretreated clinker is put into a reaction furnace, and the flow rate is 0.03m 3 Steam/h, roasting temperature is 600 ℃, defluorination time is 2h. The fluorine content after defluorination is shown in table 3.
(4) And (3) pressure cooking: the defluorinated clinker, sodium chloride and quicklime are put into a high-pressure reaction kettle together, and are boiled under pressure for 6 hours at 200 ℃ to fully dissolve out lithium.
(5) Separating and purifying: separating the mother liquor obtained by pressure boiling from slag, adding active carbon and caustic soda (the mass ratio of the caustic soda to lithium in the mother liquor is 1.2:1), fully stirring, filtering again, and collecting filtrate.
(6) Carbonizing and precipitating lithium: introducing CO into the purified filtrate 2 And (5) carbonizing and precipitating lithium until the pH value of the filtrate reaches 11.
(7) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium, collecting filter residues, and repeatedly washing to obtain crude lithium carbonate.
The leaching rate of lithium in this example was analyzed by the quality of the lithium carbonate obtained, and the results are shown in Table 2.
Example 7
The lepidolite crude ore is put into a jaw crusher for crushing, then ball-milled for 6 hours, and sieved, and ore powder with the granularity of 200 meshes is selected.
(1) High energy mechanical activation: the lepidolite ore powder is put into a high-energy ball mill, and activator oxalic acid (the mass ratio of the activator oxalic acid to the lepidolite is 0.06:1) is added, and the pore-forming agent ammonium carbonate (the mass ratio of the pore-forming agent ammonium carbonate to the lepidolite is 0.05:1) is subjected to high-energy ball milling, wherein the rotating speed is set to 1000r/min, and the ball milling time is 6 hours.
(2) High-temperature pretreatment: the composites subjected to high energy mechanical activation were pre-sintered at 600 ℃ for 4 hours.
(3) Roasting and defluorination: the pretreated clinker is put into a reaction furnace, and the flow rate is 0.05m 3 And/h of water vapor, wherein the roasting temperature is 800 ℃, and the defluorination time is 4h. The fluorine content after defluorination is shown in table 3.
(4) And (3) pressure cooking: the defluorinated clinker, sodium chloride and quicklime are put into a high-pressure reaction kettle together, and are boiled under pressure for 12 hours at 300 ℃ to fully dissolve out lithium.
(5) Separating and purifying: separating the mother liquor obtained by pressure boiling from slag, adding active carbon and caustic soda (the mass ratio of the caustic soda to lithium in the mother liquor is 1.5:1), fully stirring, filtering again, and collecting filtrate.
(6) Carbonizing and precipitating lithium: introducing CO into the purified filtrate 2 And (5) carbonizing and precipitating lithium until the pH value of the filtrate reaches 11.
(7) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium, collecting filter residues, and repeatedly washing to obtain crude lithium carbonate.
The leaching rate of lithium in this example was analyzed by the quality of the lithium carbonate obtained, and the results are shown in Table 2.
TABLE 2
TABLE 3 Table 3
Therefore, the invention adopts the combination method of the surfactant and the pore-forming agent, and is matched with the high-energy ball milling activation and defluorination roasting process, thereby obviously reducing the fluorine content in the defluorination clinker and improving the leaching rate of lithium.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. The process for improving the lithium leaching rate in lepidolite is characterized by comprising the following steps of:
(1) High-energy ball milling activation: adding an activating agent and a pore-forming agent into lepidolite ore powder for high-energy ball milling; the activator is one or more of oxalic acid, boric acid and phosphoric acid; the pore-forming agent is one or more of ammonium carbonate, ammonium chloride, ammonium nitrate, sodium carbonate, sodium bicarbonate and potassium carbonate; the mass ratio of the activator to the lepidolite ore powder is 0.02-0.06: 1, a step of; the mass ratio of the pore-forming agent to the lepidolite ore powder is 0.01-0.05: 1, a step of; the high-energy ball milling is carried out by using a high-energy ball mill; the rotating speed of the high-energy ball milling is 700r/min-1200r/min, and the time is 1h-6h;
(2) Presintering: presintering the composite material activated by high-energy ball milling in the step (1);
(3) Roasting and defluorination: introducing water vapor into the clinker pre-sintered in the step (2), and roasting and defluorinating the clinker;
(4) And (3) pressure cooking: mixing the roasted defluorinated clinker in the step (3) with leaching auxiliary materials, and carrying out pressure cooking reaction;
(5) Separating and purifying: separating the mother liquor obtained in the step (4) from slag, adding active carbon and caustic soda into the mother liquor, stirring, filtering and collecting filtrate;
(6) Carbonizing and precipitating lithium: introducing CO into the filtrate separated and purified in the step (5) 2 Carbonizing and precipitating lithium until the PH value of the filtrate reaches 11-12;
(7) Collecting lithium carbonate: filtering the suspension after carbonization and precipitation of lithium in the step (6), collecting filter residues, and washing to obtain crude lithium carbonate.
2. The process for increasing the leaching rate of lithium from lepidolite according to claim 1, wherein the lepidolite ore powder in step (1) has a particle size of 100 mesh to 300 mesh; the lepidolite ore powder is obtained by crushing and pulverizing lepidolite; the apparatus for crushing and pulverizing comprises one or more of the following: jaw crusher, twin roll mill, cone crusher, sand making machine, hammer crusher, planetary ball mill, high energy ball mill, rotary drum ball mill.
3. The process for increasing the leaching rate of lithium in lepidolite according to claim 1, wherein the pre-sintering temperature in step (2) is 200 ℃ -600 ℃ for 30min-4h.
4. The process for increasing the leaching rate of lithium in lepidolite according to claim 1, wherein the steam in the step (3) is introduced in an amount of 0.01m per ton of clinker 3 /h-0.5m 3 /h; the roasting defluorination temperature is 400-1000 ℃ and the time is 30min-4h.
5. The process for increasing the leaching rate of lithium in lepidolite according to claim 1, wherein the leaching auxiliary material in step (4) is a mixture of a leaching agent and a precipitating agent.
6. The process of claim 5, wherein the leaching agent comprises one or more of sodium chloride, ferric chloride, cupric chloride, manganese chloride, nickel chloride, calcium chloride, zinc chloride, sodium sulfate, ferric sulfate, cupric sulfate, manganese sulfate, nickel sulfate, and zinc sulfate;
the precipitant comprises one or more of calcium oxide, calcium hydroxide and quicklime.
7. The process for increasing the leaching rate of lithium in lepidolite according to claim 1, wherein the temperature of the autoclaving reaction in step (4) is 120-300 ℃ for 2-12h.
8. The process for improving the leaching rate of lithium in lepidolite according to claim 1, characterized in that the mass ratio of caustic soda to lithium in the mother liquor in step (5) is 1.1-1.5:1, a step of; the mass ratio of the active carbon to lithium in the mother solution is 0.02-0.1:1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210212875.2A CN114752784B (en) | 2022-03-04 | 2022-03-04 | Technology for improving lithium leaching rate in lepidolite |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210212875.2A CN114752784B (en) | 2022-03-04 | 2022-03-04 | Technology for improving lithium leaching rate in lepidolite |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114752784A CN114752784A (en) | 2022-07-15 |
CN114752784B true CN114752784B (en) | 2023-06-20 |
Family
ID=82326023
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210212875.2A Active CN114752784B (en) | 2022-03-04 | 2022-03-04 | Technology for improving lithium leaching rate in lepidolite |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114752784B (en) |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101302018B (en) * | 2008-07-02 | 2010-08-11 | 江西赣锋锂业股份有限公司 | Method for preparing lithium carbonate by extracting lithium from lepidolite |
CN101328021B (en) * | 2008-07-22 | 2010-12-08 | 内蒙古科技大学 | Porous devitrified glass and manufacturing method thereof |
CN101892394B (en) * | 2009-12-18 | 2013-07-24 | 中南大学 | Method and device for extracting lithium from lithium mica |
CN102586587B (en) * | 2012-03-24 | 2013-10-23 | 宜春合纵锂业科技有限公司 | Method for treating lepidolite ore |
CN105036718A (en) * | 2015-06-25 | 2015-11-11 | 廖建彬 | Fuel-oil-activating combustion-supporting infrared radiation material as well as preparation method and application thereof |
CN107117940A (en) * | 2017-04-24 | 2017-09-01 | 东莞市佳乾新材料科技有限公司 | A kind of porous material based on modified steel scoria and preparation method thereof |
CN107475537B (en) * | 2017-07-17 | 2019-03-19 | 江西南氏锂电新材料有限公司 | The method of lithium, rubidium, cesium salt is extracted from lepidolite raw material |
CN109368614A (en) * | 2018-10-25 | 2019-02-22 | 江苏大学 | A kind of preparation process and application thereof of the porous defect carbon material derived from petroleum coke |
CN111847488A (en) * | 2020-08-03 | 2020-10-30 | 柴肖芳 | Process for extracting lithium from lepidolite |
CN112624161B (en) * | 2020-12-31 | 2022-11-01 | 江西南氏锂电新材料有限公司 | Method for preparing lithium carbonate by extracting lithium from mechanically activated lepidolite |
-
2022
- 2022-03-04 CN CN202210212875.2A patent/CN114752784B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN114752784A (en) | 2022-07-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111170343B (en) | Method for recovering and producing lithium hydroxide from waste lithium ion battery | |
CN100469697C (en) | Method for producing low-magnesium battery-stage lithium carbonate from lithium sulfate solution | |
CN114394582B (en) | Method for regenerating ferric phosphate from lithium-extracted ferrophosphorus slag | |
CN113651342A (en) | Method for producing lithium product by processing lepidolite through nitric acid atmospheric pressure method | |
CN110510642A (en) | A kind of method that low-grade α spodumene economy mentions lithium | |
CN112310499B (en) | Recovery method of waste lithium iron phosphate material and obtained recovery liquid | |
CN114890443A (en) | System and process method for high-value utilization of lithium-containing waste | |
KR20240096445A (en) | Method for producing carbon-coated sodium iron fluorophosphate from spent lithium iron phosphate and its application | |
CN113045060A (en) | Comprehensive utilization method of seawater resources | |
CN114752784B (en) | Technology for improving lithium leaching rate in lepidolite | |
CN111074076B (en) | Comprehensive utilization system and method for metallurgical solid waste | |
CN117693606A (en) | Method for selectively extracting lithium from waste lithium ion battery powder by aluminum-carbon co-reduction | |
WO2023193517A1 (en) | Method for treating copper-cobalt alloy of waste lithium battery and use thereof | |
CN116995327A (en) | Method for recycling lithium from ternary positive electrode waste | |
CN116411182A (en) | Method for selectively recovering lithium from lithium battery | |
CN116262948A (en) | Method for activating clay type lithium ore and extracting lithium ions | |
CN114006067B (en) | Method and system for recycling anode and cathode mixed powder of waste ternary lithium ion battery | |
CN116497235A (en) | Method for extracting lithium from low-lithium clay | |
CN113060741B (en) | Method for comprehensively utilizing boron-extracted iron tailings from ludwigite | |
CN113999993A (en) | Method for recovering anode and cathode mixed powder of waste ternary lithium ion battery | |
CN116240400B (en) | Method for efficiently extracting lithium from lepidolite lithium extraction waste residue at low temperature | |
CN110563009A (en) | Method for preparing battery-grade lithium carbonate from fly ash by carbonization decomposition method | |
CN118495566A (en) | Method for recycling and preparing battery-grade lithium carbonate and ferric phosphate by using waste lithium iron phosphate battery | |
CN114525408B (en) | Method for combined treatment of waste lithium cobalt oxide anode material and tungsten-containing solid waste | |
CN116534905B (en) | Method for recycling valuable metals in waste lithium cobaltate by utilizing carbon-containing crude ferric phosphate generated after selective lithium extraction of lithium iron phosphate |
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 |