CN118207426A - Method for extracting lithium by composite roasting and leaching of clay type lithium ore - Google Patents
Method for extracting lithium by composite roasting and leaching of clay type lithium ore Download PDFInfo
- Publication number
- CN118207426A CN118207426A CN202410385281.0A CN202410385281A CN118207426A CN 118207426 A CN118207426 A CN 118207426A CN 202410385281 A CN202410385281 A CN 202410385281A CN 118207426 A CN118207426 A CN 118207426A
- Authority
- CN
- China
- Prior art keywords
- lithium
- leaching
- roasting
- ores
- ore
- 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.)
- Pending
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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (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)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for extracting lithium by composite roasting and leaching of clay type lithium ores, which comprises the steps of crushing clay type lithium ores, metering one or more of ammonium bisulfate, sodium bisulfate, ammonium sulfate and sodium sulfate, grinding together, and then adding water and/or sulfuric acid to uniformly mix to obtain granular particle materials; roasting the granular particle material at a proper temperature to obtain a roasted ore; grinding the sintered ore, adding clear water, heating to 40-90 ℃ for leaching, filtering, washing, removing impurities from the filtrate, and crystallizing and precipitating to obtain the lithium carbonate. The invention creatively develops a special medicament formula, and under proper roasting conditions, lithium in the lithium-containing mineral is replaced by cations with small ionic radius, so that the lithium-containing mineral is converted into lithium sulfate which is easily dissolved in water, the roasting conditions are controlled, the leaching of impurities such as aluminum, iron and the like is reduced, the selective leaching and extraction of lithium are realized, the concentration of soluble salt is obviously reduced, and an important foundation is laid for improving the concentration of lithium in leaching liquid and reducing the production cost by cyclic leaching.
Description
Technical Field
The invention relates to a lithium extraction method, in particular to a clay type lithium ore composite roasting leaching lithium extraction method.
Background
Lithium is widely used in the industries of batteries, ceramics, glass, lubricants, refrigerating fluids, nuclear industry, photoelectricity and the like. With the continuous development of electronic products such as computers, digital cameras, mobile phones, mobile electric tools, etc., the battery industry has become the largest consumer field of lithium. In addition, lithium carbonate is one of the effective ways of reducing energy consumption and protecting environment in the ceramic industry, and the demand for lithium is also increased. At the same time, various new roles of lithium in glass are being discovered, and the demand for lithium in the glass industry will remain increasing. Thus, the glass and ceramic industry is the second largest consumer area for lithium.
Lithium is known as 'twenty-first century energy metal' and 'twenty-first century clean energy', is an ideal electrode material of a battery, is a core metal for supporting the development of new lithium battery energy industry in China, and relates to the healthy and stable development of new energy automobiles, energy storage, electronic information and other strategic emerging industries in China in terms of safe supply.
The lithium content in the crust is about 0.0065%, and there are 150 or more known lithium-containing minerals, mainly in the form of spodumene, lepidolite, petalite, and the like. The global lithium mineral deposits are mainly of five types, namely, pegmatite mineral deposits, brine mineral deposits, seawater mineral deposits, hot spring mineral deposits and stacked mineral deposits, and the lithium resources utilized in the current exploitation are mainly pegmatite mineral deposits and brine mineral deposits.
The lithium resources in salt lake brine account for about 90% of the world's established lithium resources, and are mainly distributed in bolivia, chile, argentine, china and the united states. The dita's alta horses (SALAR DE ATACAMA), the bolivia's Wu Youni (Salar de Uyuni), the Argentina's Weng Bulei Moire, the U.S. silver peaks, the Tibetan zabujer of China and the Qinghai salt lake are salt lakes with abundant lithium resources which have been identified worldwide.
The granite peganum salt deposit is mainly distributed in australia, canada, finland, china, zimbabwe, south africa, congo, although peganum salt deposit is also found in india and france, but has no commercial exploitation value. In particular, global spodumene ore is predominantly distributed in australia, canada, zimbabwe, congo, brazil and china; lepidolite ore is predominantly distributed in zimbabwe, canada, the united states, mexico and china.
The Chinese lithium resource is mainly in the form of salt lake, but is limited to the technical and cost reasons, the current lithium source is still mainly extracting lithium from ores, the method belongs to the imported state of the lithium resource, and the searching and developing of new lithium resource become urgent matters in China.
Clay-type lithium ores are new types of lithium resources that have made significant development in recent years in Guizhou province, and there are mainly two types: firstly, a new type of lithium ore deposit is formed by newly discovered gas-liquid fluid bottom cleavage, and the lithium-containing minerals are mainly lithium chlorite. And secondly, clay rock type lithium ore deposit is associated with the aluminum-containing rock system, wherein the lithium-containing minerals can be clay minerals such as illite, kaolinite, montmorillonite and the like. The gas-liquid fluid bottom split type lithium ore newly discovered by the Guizhou lithium ore has the greatest potential and relatively high grade.
The main methods for extracting lithium from salt lake brine include a precipitation method, a solvent extraction method, an adsorption method and the like, wherein the most main methods are a carbonate precipitation method, and the method has the advantages of low energy consumption and becomes a main flow method for treating salt lake brine with a low magnesium-lithium ratio; the method has the defects of high consumption of alkali and certain limitation on the selectivity of lithium for the high-magnesium-lithium ratio type salt lake.
Most of the hard rock type lithium deposits are granite type ore deposits and alkaline feldspar granite type ore deposits, and the resource reserves are found to account for about 20% of the total national lithium resources reserves. Although the content of the lithium resource is not as high as that of brine, the process is more mature than the development of extracting lithium from brine, and spodumene has high lithium content (the theoretical lithium oxide content can reach 8.03 percent) and is easy to treat, so that the process is a main raw material for extracting lithium from hard rock type lithium ores at present, and lepidolite is the next step. The main processes of separating and extracting lithium from hard rock type lithium ore include sulfate process, sulfuric acid process, limestone sintering process, chloridizing roasting process, soda ash pressing and boiling process, hydrofluoric acid process, etc. the main processes are physical and chemical treatment to convert lithium from lithium ore into soluble salt, leaching, purifying, etc. to synthesize lithium product.
The deposition type lithium ores are mainly distributed in the United states, mexico, selvia and other countries, and in southwest regions of China. The deposition type lithium ores in China are mainly distributed in regions such as Yunnan, guizhou, guangxi and the like, and have great differences from the existing deposition type lithium ores in foreign countries in main material compositions, lithium occurrence states, ore formation conditions and the like. The lithium extraction process of the deposit type lithium ore mainly comprises the processes of direct water/acid leaching, roasting-leaching, auxiliary roasting-leaching, chlorination-vulcanization and the like. The sulfuric acid leaching process of the deposit type lithium ore can lead the extraction rate of lithium to reach 89%, and the leaching condition of impurity elements such as aluminum, magnesium, iron, silicon and the like in the acid leaching process is not clear at present. The lithium leaching rate of the roasting-leaching process is more than 80%, and the main defects of the process are high roasting temperature, high energy consumption, high cost and high separation and purification difficulty in the later stage. The chlorination-vulcanization process reaction device has higher control difficulty and higher cost.
The Guizhou lithium resource is different from the halogen water type and hard rock type lithium ore resource, the grade is low, the beneficiation difficulty is high, the research and development degree is very low, and most of researches are still in a laboratory stage. Because the clay type lithium ore has low grade, the lithium-loaded mineral is mainly lithium chlorite, the embedding granularity is fine, and high-grade concentrate is difficult to obtain through beneficiation and enrichment. The current research work is mainly focused on the aspect of direct metallurgical extraction technology, and the main technology of research is roasting-leaching technology, acidification roasting leaching technology, ammonium salt roasting leaching technology and the like, and the problems of large slag quantity, large acid consumption, high cost and the like exist in the technologies generally.
Disclosure of Invention
The invention aims to provide a method for extracting lithium by composite roasting and leaching of clay-type lithium ores. The invention mainly aims at the defects of the process, creatively develops a special medicament formula according to the characteristics that the main lithium-carrying mineral of the clay type lithium ore is clay mineral such as lithium chlorite, and the like, and under the proper roasting condition, utilizes cations with small ionic radius to replace lithium in the lithium-containing mineral to convert the lithium into lithium sulfate which is easily dissolved in water, controls the roasting condition, reduces the leaching of impurities such as aluminum, iron and the like, remarkably reduces the concentration of soluble salt while realizing the selective leaching and extraction of the lithium, and lays an important foundation for improving the concentration of the lithium in the leaching liquid and reducing the production cost by the cyclic leaching.
The technical scheme of the invention is as follows: a method for extracting lithium by composite roasting and leaching of clay type lithium ore comprises the steps of crushing clay type lithium ore, metering one or more of ammonium bisulfate, sodium bisulfate, ammonium sulfate and sodium sulfate with the ore amount of 5-60% to be milled together, and then adding water with the ore amount of 5-20% and/or sulfuric acid with the ore amount of 10-40% to be uniformly mixed to prepare granular particle materials; roasting the granular particle material at 400-800 ℃ for 1-3 hours to obtain a roasted ore; grinding the calcined ore, adding clear water with the amount of 2-4 times of that of the raw ore, heating to 40-90 ℃ for leaching for 0.5-3 hours, filtering, washing, removing impurities from filtrate, and finally boiling, crystallizing and precipitating with sodium carbonate to obtain the lithium carbonate.
In the method for extracting lithium by composite roasting and leaching of clay-type lithium ores, the clay-type lithium ores are crushed to the granularity of-5 mm.
In the method for extracting lithium by composite roasting and leaching of clay-type lithium ores, one or more of ammonium bisulfate, sodium bisulfate, ammonium sulfate and sodium sulfate, the amount of which is 5-20% of that of the ores, are metered in the grinding process, and the grinding is carried out until the granularity of the powder is-0.10 mm, wherein the granularity of the powder accounts for 60-90% of the total materials.
In the method for extracting lithium by composite roasting and leaching of clay type lithium ores, the filtrate impurity removal treatment specifically comprises the following steps: adding ammonium sulfate and/or calcium carbonate into the filtrate to remove aluminum, iron and manganese impurities, removing magnesium and manganese impurities from the calcium oxide suspension, removing calcium impurities from sodium carbonate, deeply removing impurities by ion exchange, and finally boiling, crystallizing and precipitating with sodium carbonate to obtain the lithium carbonate.
In the method for extracting lithium by composite roasting and leaching of clay-type lithium ores, the concentration of sulfuric acid is 98.3%.
The invention has the beneficial effects that: compared with the prior art, the method has the advantages that the small-radius ions such as hydrogen ions, ammonium ions and sodium ions in the bisulfate are utilized, the small-radius ions such as the hydrogen ions, the ammonium ions and the sodium ions and the lithium-carrying minerals are promoted to generate the ion exchange effect through the roasting effect under the proper condition, the lithium ions in the lithium-carrying minerals are replaced, so that lithium in the ores is converted into lithium sulfate which is easily dissolved in water, and the lithium sulfate is dissolved by clear water and enters the solution, so that the separation and extraction of lithium are realized. By utilizing the characteristics that the decomposition temperature of ammonium bisulfate is lower, and the ammonium bisulfate is decomposed into ammonia, nitrogen, water, sulfur dioxide, sulfur trioxide and other components at a higher temperature to enter the flue gas, the lithium sulfate generated by roasting is ensured not to enter insoluble minerals again due to chemical balance movement by utilizing the small radius of sodium ions and the higher decomposition temperature of sodium sulfate. The combined action of the ammonium salt and the sodium salt can obviously reduce the concentration of sodium ions in the leaching lithium extraction solution while ensuring that the leaching rate of lithium is not reduced, greatly reduce the accumulation speed of sodium ions in the process of circularly leaching and extracting lithium, and provide favorable conditions for increasing the circulating leaching times of lithium, improving the concentration of lithium in the leaching solution and reducing the production cost.
The dosage of the medicament of the method is less than about one third of that of a sulfuric acid method, the leaching rate of lithium can reach 92.04%, the content of impurity aluminum in the leaching solution is below 50mg/L, the content of iron is lower than the detection limit of a test method, the pH value of the lithium extraction leaching solution is between 4 and 5, the purpose of selectively leaching lithium is basically achieved, and an important foundation is laid for repeatedly and circularly leaching the lithium extraction solution, improving the concentration of lithium ions in the lithium extraction solution and reducing the production cost.
Ammonia and sulfur dioxide generated by roasting can be absorbed and recycled by water to prepare ammonium bisulfate or ammonium sulfate, and soluble salt can be used for preparing sodium bisulfate or sodium sulfate and is returned to be used for granulating, roasting and recycling of lithium ores.
In conclusion, the method has the advantages of low dosage of the medicament, high lithium leaching rate, easy purification and impurity removal and low production cost, has wide industrial application prospect, and has obvious innovation compared with other roasting and lithium extraction processes.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not intended to be limiting.
Example 1 of the present invention: a method for extracting lithium by composite roasting and leaching of clay-type lithium ores comprises the steps of taking 5kg of clay-type lithium ores, crushing to-5 mm, adding 3kg of ammonium bisulfate, grinding together until the granularity of-0.10 mm accounts for 60-90% of the total materials, and then adding 0.75kg of water for uniformly mixing to obtain granular particle materials; roasting the granular particle material at 450 ℃ for 3 hours to obtain a roasted ore; crushing and grinding the sintered ore, adding 15L of water into the powder, heating to 80 ℃, leaching for 2 hours, filtering, washing, removing aluminum from the filtrate by adding ammonium sulfate, adding calcium carbonate to remove iron, adding calcium oxide to remove magnesium and manganese, adding sodium carbonate to remove impurities such as calcium, further removing impurities deeply by ion exchange, and finally boiling, crystallizing and precipitating by using sodium carbonate to prepare lithium carbonate.
Example 2 of the present invention: a method for extracting lithium by composite roasting and leaching of clay-type lithium ores comprises the steps of taking 5kg of clay-type lithium ores, crushing to-5 mm, adding 1.69kg of ammonium sulfate, grinding together until the granularity of-0.10 mm accounts for 60-90% of the total materials, then adding 1.31kg of sulfuric acid and 0.6kg of water, and uniformly mixing to obtain materials; roasting the granular particle material at 450 ℃ for 2.5 hours to obtain a roasted ore; crushing and grinding the calcined ore, adding 12.5L of water into the powder, heating to 60 ℃, leaching for 1.5 hours, filtering, washing, wherein the leaching rate of lithium reaches 88.69%, removing aluminum from the filtrate by adding ammonium sulfate, adding calcium carbonate for removing iron, adding calcium oxide for removing magnesium and manganese, adding sodium carbonate for removing impurities such as calcium, further removing impurities deeply by ion exchange, and finally boiling, crystallizing and precipitating by using sodium carbonate to prepare lithium carbonate.
Example 3 of the present invention: a method for extracting lithium by composite roasting and leaching of clay-type lithium ores comprises the steps of taking 5kg of clay-type lithium ores, crushing to-5 mm, adding 0.87kg of ammonium bisulfate and 0.42kg of sodium bisulfate, grinding until the granularity of-0.10 mm accounts for 60-90% of the total materials, then adding 1.71kg of sulfuric acid and 0.5kg of water, and uniformly mixing to obtain materials; roasting the granular particle material at 750 ℃ for 3 hours to obtain a roasted ore; crushing and grinding the calcined ore, adding 10L of water into the powder, heating to 70 ℃, leaching for 1 hour, filtering, washing, wherein the leaching rate of lithium reaches 91.44%, adding calcium carbonate into filtrate to remove aluminum and iron, adding calcium oxide to remove magnesium and manganese, adding sodium carbonate to remove impurities such as calcium and the like, further removing impurities deeply through ion exchange, and finally boiling, crystallizing and precipitating with sodium carbonate to prepare lithium carbonate.
Example 4 of the present invention: a method for extracting lithium by composite roasting and leaching of clay-type lithium ores comprises the steps of taking 5kg of clay-type lithium ores, crushing to-5 mm, adding 0.25kg of ammonium sulfate and 0.25kg of sodium sulfate, grinding until the granularity of-0.10 mm accounts for 60-90% of the total materials, adding 0.75kg of sulfuric acid and 0.75kg of water, and uniformly mixing to obtain materials; roasting the granular particle material at 700 ℃ for 2 hours to obtain a roasted ore; crushing and grinding the sintered ore, adding 17.5L of water into the powder, heating to 50 ℃, leaching for 2.5 hours, filtering, washing, wherein the leaching rate of lithium reaches 92.04%, adding calcium carbonate into filtrate to remove aluminum and iron, adding calcium oxide to remove magnesium and manganese, adding sodium carbonate to remove impurities such as calcium and the like, further removing impurities deeply through ion exchange, and finally boiling, crystallizing and precipitating with sodium carbonate to prepare lithium carbonate.
Example 5 of the present invention: a method for extracting lithium by composite roasting and leaching of clay-type lithium ores comprises the steps of taking 5kg of clay-type lithium ores, crushing to-5 mm, adding 0.44kg of ammonium bisulfate and 0.25kg of sodium sulfate, grinding until the granularity of-0.10 mm accounts for 60-90% of the total materials, adding 0.5kg of sulfuric acid and 0.8kg of water, and uniformly mixing to obtain materials; roasting the granular particle material at 700 ℃ for 1.5 hours to obtain a roasted ore; crushing and grinding the sintered ore, adding 20L of water into the powder, heating to 90 ℃, leaching for 3 hours, filtering, washing, removing aluminum and iron from the filtrate by adding calcium carbonate, removing magnesium and manganese by adding calcium oxide, removing impurities such as calcium by adding sodium carbonate, deeply removing impurities by ion exchange, and finally boiling, crystallizing and precipitating by using sodium carbonate to prepare lithium carbonate.
In the embodiment, the filter residue after leaching and filtering is subjected to harmless recycling treatment. And the flue gas in the roasting process is absorbed by water or hydrogen peroxide to prepare ammonium bisulfate, and the ammonium bisulfate is returned to be used for lithium ore roasting granulation recycling. And after sodium ions in the lithium circulating leaching solution are accumulated to a certain extent, evaporating and concentrating to prepare sodium sulfate, and returning the sodium sulfate for roasting, granulating and recycling of lithium ores.
The main chemical reaction equations of the roasting process of the invention are as follows:
2LiAl 4(Si3Al)O10(OH)8 (lithium chlorite) )+2NH4HSO4＝2NH4Al4(Si3Al)O10(OH)8+Li2SO4+SO3↑+H2O↑(1)
2LiAl 4(Si3Al)O10(OH)8 (lithium chlorite) )+2NaHSO4＝2NaAl4(Si3Al)O10(OH)8+SO3↑+Li2SO4+H2O↑(2)
2LiAl 4(Si3Al)O10(OH)8 (lithium chlorite) )+16H2SO4＝Li2SO4+5Al2(SO4)3+6SiO2+24H2O (3)
3NH4HSO4＝NH3+N2↑+3SO2↑+6H2O↑ (4)
NH3+SO3+H2O＝NH4HSO4 (5)
NH3+SO2+H2O2＝NH4HSO4 (6)
From the above chemical reaction and the results of practical experimental study, it was shown that:
(1) The single sulfating roasting leaching method is used for extracting lithium, has strong sulfuric acid acidity, strong leaching capacity and high leaching rate of lithium, and simultaneously, a large amount of aluminum, iron and other impurities are also soaked into the solution, so that great difficulty is brought to subsequent impurity removal. The invention adopts one or more of solid additives such as ammonium bisulfate, sodium bisulfate, ammonium sulfate, sodium sulfate and the like to be milled with ore, and then sulfuric acid and/or water are mixed with mineral powder uniformly, granulated, roasted and leached to extract lithium. The solid additive is added to react with sulfuric acid to generate ammonium bisulfate and sodium bisulfate, so that the acidity of the sulfuric acid is obviously reduced, the roasting and leaching capacity of the sulfuric acid is reduced, and the leaching of aluminum and iron ions in ores is greatly reduced. The impurity content in the lithium extraction solution is obviously reduced, the dosage of the medicament is reduced, and the lithium extraction cost is reduced.
(2) When studying ammonium bisulfide roasting and leaching to extract lithium, the method finds that the amount of impurities such as aluminum, iron and the like entering the leaching solution is much lower than that of single sulfating roasting and leaching to extract lithium, but during cyclic leaching, the impurities such as aluminum, iron and the like are rapidly accumulated, and the cyclic leaching times of the lithium extracting solution are still severely limited. The roasting temperature of ammonium bisulfate is increased, so that the content of impurities such as aluminum, iron and the like in the lithium extraction leaching solution can be obviously reduced, but the leaching rate of lithium is also reduced more, which is probably caused by the fact that the decomposition temperature of ammonium salt is lower and the substances exchanged with lithium at high temperature are decomposed again. In the invention, a proper amount of sodium sulfate or sodium bisulfate is added into a sulfuric acid-ammonium sulfate roasting system, so that ammonium ions and sodium ions with smaller radius are fully utilized, the radius of the ammonium ions is closer to that of lithium ions, the ammonium bisulfate and the sodium bisulfate can exchange ions with lithium-carrying minerals in clay-type lithium ores at a proper roasting temperature, the decomposition temperature of the ammonium bisulfate is lower, the decomposition temperature of the sodium bisulfate is higher, lithium is extracted by roasting at a higher temperature, ammonium salts are easy to decompose and enter roasting smoke, and sodium salts are difficult to decompose and enter a lithium extracting solution, thereby obviously reducing the accumulation of sodium ions in the lithium extracting solution by leaching.
(3) The dosage of the medicament is only about one fourth of that of a sulfuric acid method, the content of impurity aluminum in the leaching solution is below 50mg/L, the content of iron is lower than the detection limit of a test method, the pH value of the lithium extraction leaching solution is between 4 and 5, the purification and impurity removal of the lithium extraction solution are very easy, and an important foundation is laid for repeatedly and circularly leaching the lithium extraction solution to improve the concentration of lithium ions in the lithium extraction solution. The invention has the advantages of low dosage of the medicament, high lithium leaching rate, easy purification and impurity removal, low production cost, wide industrial application prospect and obvious innovation compared with other roasting and lithium extraction processes.
In order to verify the effect of the method according to the invention, the following tests were carried out. Under the optimized conditions, the roasting and leaching effects of sulfuric acid, sulfuric acid+sodium sulfate, sulfuric acid+ammonium bisulfate+sodium bisulfate are compared with those of the conditions shown in Table 1.
Table 1 comparison Table of lithium extraction effects of roasting and leaching of different medicament systems
As can be seen from the comparison of the results in Table 1, the total amount of the agent in the sulfuric acid+ammonium bisulfate+sodium bisulfate system is equivalent to that in the sulfuric acid+sodium sulfate system, except for 30% of the sulfuric acid system. The lithium leaching rate of the sulfuric acid, ammonium bisulfate and sodium bisulfate system is slightly lower than that of the sulfuric acid, sodium sulfate system and sulfuric acid system, but the leaching rate of iron and aluminum is far lower than that of the sulfuric acid, sodium sulfate system and far lower than that of the sulfuric acid system, which lays an important foundation for the repeated cyclic leaching of lithium leaching solution. Test results prove that the leaching liquid of the sulfuric acid system can be leached circularly for 1 time, the leaching liquid of the sulfuric acid and sodium sulfate system can be leached circularly for 5 times, and the leaching liquid of the sulfuric acid and ammonium bisulfate and sodium bisulfate system can be leached circularly for nearly 30 times due to low iron and aluminum impurities and the assistance of ores or tailings containing calcite or dolomite.
Compared with sulfuric acid system, the method of the invention obviously reduces the dosage of roasting medicament and greatly saves medicament cost.
Compared with a sulfuric acid and sodium sulfate system, the method provided by the invention has the advantages that the content of impurities such as iron and aluminum in the leaching solution is obviously reduced, the purpose of selectively leaching and extracting lithium is achieved, the water consumption for extracting lithium by leaching is obviously saved, the concentration of lithium in the leaching solution is improved, the high-energy consumption concentration process is avoided, and an important foundation is laid for reducing the production cost.
In the formation process of the method, the technical problem is that a great amount of aluminum, iron, manganese and other impurities are leached out while lithium in the roasted ore is leached out, so that great difficulty is brought to subsequent purification and impurity removal, and the consumption of sulfuric acid is too large and is equivalent to the ore amount. Although aluminum sulfate and potassium aluminum sulfate double salt crystallization precipitation are adopted to remove aluminum, calcium carbonate or lime precipitation to remove iron are adopted to study, products with good quality such as aluminum potassium sulfate can be obtained, aluminum ions in the lithium extraction solution are easy to accumulate, the cyclic leaching is quite unfavorable, the concentration of lithium ions in the lithium extraction solution cannot be improved, the concentration of lithium ions in the lithium extraction solution has to be improved by adopting evaporation concentration, so that lithium carbonate products can be conveniently prepared, the evaporation concentration energy consumption is extremely high, and the production cost of the lithium carbonate products is greatly improved. The calcium carbonate or lime is precipitated to remove iron, so that lithium is greatly lost along with the precipitation of iron, and the lithium cannot be recovered, and the economy of extracting lithium is reduced.
Through the full research on the properties of clay type lithium ore and the analysis on the roasting and leaching mechanism of sulfuric acid, the method is considered to be strong in sulfuric acid acidity and strong in leaching capability, so that impurities such as aluminum, iron, manganese and the like in the ore are leached in a large amount. The ammonium bisulfate is adopted as a roasting and leaching agent of clay type lithium ores, so that the acidity of sulfuric acid is obviously reduced, the roasting and leaching capacity of sulfuric acid is reduced, and the leaching rate of aluminum and iron ions in the ores is greatly reduced. However, impurity ions such as aluminum, iron and the like can be rapidly accumulated in the cyclic leaching process, so that the cyclic leaching times of the lithium extraction solution are limited, and the concentration of lithium ions in the lithium extraction solution is limited.
In order to further reduce the concentration of impurity ions such as aluminum and iron in the lithium extraction leaching solution, the decomposition of substances such as aluminum sulfate and iron sulfate formed in the roasting process into water-insoluble oxides such as aluminum oxide and ferric oxide is promoted by increasing the roasting temperature, and although the method can remarkably reduce the content of impurities such as aluminum and iron ions in the lithium extraction leaching solution, the leaching rate of lithium is also reduced considerably, presumably the decomposition temperature of ammonium salt is lower, and the substances exchanged with lithium at high temperature are decomposed again.
In order to reduce the content of impurities such as aluminum and iron ions in the lithium extraction leaching solution and ensure that the leaching rate of lithium is not reduced or is reduced little, sodium sulfate with higher decomposition temperature and smaller cation radius is added into an ammonium bisulfate roasting system based on analysis of a ammonium bisulfate roasting leaching lithium extraction mechanism, and roasting and leaching lithium is carried out at a higher temperature. As expected, the addition of sodium sulfate reduces the content of aluminum, iron ions and other impurities in the lithium extraction leaching solution, and simultaneously ensures the leaching rate of lithium, thereby achieving the purpose of selectively leaching and extracting lithium.
Meanwhile, the combination of the bisulfate which is easy to decompose and the bisulfate which is difficult to decompose at a higher temperature solves the main problems of high acid consumption, high impurity leaching amount, high impurity removal difficulty, high cost and the like. According to the characteristics that the main lithium-carrying minerals of the clay-type lithium ore are clay minerals such as lithium chlorite, sulfuric acid, sulfate or bisulfate with small ionic radius are creatively added into the ore, and through roasting, the ion exchange effect of small-radius ions such as hydrogen ions, ammonium ions, sodium ions and the like in the sulfuric acid, sulfate and the lithium-carrying minerals is promoted, so that lithium ions in the lithium-carrying minerals are replaced, lithium in the ore is converted into lithium sulfate salt which is easy to dissolve in water and enters a solution by clear water, and separation and extraction of lithium are realized. Ammonium bisulfate and sodium bisulfate are adopted as roasting medicaments, so that the acidity of sulfuric acid is obviously reduced, the roasting leaching capacity of the sulfuric acid is reduced, the leaching of aluminum and iron ions in ores is greatly reduced, the medicament dosage is reduced, and the lithium extraction cost is reduced. Particularly, ammonium sulfate or ammonium bisulfate is added, at a lower temperature, ammonium ions and hydrogen ions effectively obtain lithium ions to form lithium sulfate which is easy to dissolve in water, and at a higher temperature, the ammonium sulfate or ammonium bisulfate is decomposed to generate gases such as ammonia, nitrogen, water, sulfur dioxide and the like to enter a gas phase, so that the concentration of impurities entering a liquid phase in a leaching process is greatly reduced, the impurity removal difficulty is reduced, and the cycle leaching times are improved. Meanwhile, the roasting reaction is controlled to be carried out at a higher temperature, so that impurities such as aluminum sulfate, ferric sulfate and the like generated in the roasting process are promoted to be decomposed into substances such as aluminum oxide, ferric oxide and the like which are difficult to leach by clear water, excessive impurities are prevented from entering the lithium extraction leaching solution, and the purpose of selectively leaching and extracting lithium is achieved. The method lays an important foundation for improving the concentration of lithium in the leaching solution and reducing the production cost by cyclic leaching.
Claims (5)
1. A method for extracting lithium by composite roasting and leaching of clay type lithium ores is characterized by comprising the following steps: crushing clay type lithium ores, metering one or more of ammonium bisulfate, sodium bisulfate, ammonium sulfate and sodium sulfate with the amount of 5-60% of the ores, grinding the materials together, and then adding water with the amount of 5-20% of the ores and/or sulfuric acid with the amount of 10-40% of the ores to uniformly mix the materials to prepare granular particle materials; roasting the granular particle material at 400-800 ℃ for 1-3 hours to obtain a roasted ore; grinding the calcined ore, adding clear water with the amount of 2-4 times of that of the raw ore, heating to 40-90 ℃ for leaching for 0.5-3 hours, filtering, washing, removing impurities from filtrate, and finally boiling, crystallizing and precipitating with sodium carbonate to obtain the lithium carbonate.
2. The method for extracting lithium by composite roasting and leaching of clay-type lithium ores, which is characterized by comprising the following steps of: the clay-type lithium ore is crushed to a granularity of-5 mm.
3. The method for extracting lithium by composite roasting and leaching of clay-type lithium ores, which is characterized by comprising the following steps of: in the grinding process, one or more of ammonium bisulfate, sodium bisulfate, ammonium sulfate and sodium sulfate accounting for 5-20% of the ore amount are metered and ground together until the granularity of-0.10 mm accounts for 60-90% of the total materials.
4. The method for extracting lithium by composite roasting and leaching of clay-type lithium ores, which is characterized by comprising the following steps of: the filtrate impurity removal treatment specifically comprises the following steps: adding ammonium sulfate and/or calcium carbonate into the filtrate to remove aluminum, iron and manganese impurities, removing magnesium and manganese impurities from the calcium oxide suspension, removing calcium impurities from sodium carbonate, deeply removing impurities by ion exchange, and finally boiling, crystallizing and precipitating with sodium carbonate to obtain the lithium carbonate.
5. The method for extracting lithium by composite roasting and leaching of clay-type lithium ores, which is characterized by comprising the following steps of: the sulfuric acid concentration was 98.3%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410385281.0A CN118207426A (en) | 2024-04-01 | 2024-04-01 | Method for extracting lithium by composite roasting and leaching of clay type lithium ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410385281.0A CN118207426A (en) | 2024-04-01 | 2024-04-01 | Method for extracting lithium by composite roasting and leaching of clay type lithium ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118207426A true CN118207426A (en) | 2024-06-18 |
Family
ID=91448758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410385281.0A Pending CN118207426A (en) | 2024-04-01 | 2024-04-01 | Method for extracting lithium by composite roasting and leaching of clay type lithium ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118207426A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118880064A (en) * | 2024-07-17 | 2024-11-01 | 昆明理工大学 | A method for low-temperature acid-free leaching of lithium from clay-type lithium ore |
-
2024
- 2024-04-01 CN CN202410385281.0A patent/CN118207426A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118880064A (en) * | 2024-07-17 | 2024-11-01 | 昆明理工大学 | A method for low-temperature acid-free leaching of lithium from clay-type lithium ore |
| CN118880064B (en) * | 2024-07-17 | 2025-02-18 | 昆明理工大学 | Method for leaching lithium from clay-type lithium ore at low temperature in acid-free manner |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108075202B (en) | Comprehensive recovery method of lithium iron phosphate anode material | |
| CN103266224B (en) | A kind of ion adsorption type re extracting method | |
| CN115216645B (en) | Method for extracting lithium from electrolytic aluminum waste residue by mixed salt calcination | |
| CN102828025B (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN104046800B (en) | A kind of from containing the technique extracting white tungsten fine ore ferberite or tungstenic waste residue | |
| CN110885090A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method | |
| CN105293564A (en) | Method for recycling zinc-containing dust ash in steel plant | |
| CN114875250B (en) | Method for purifying lithium from lithium-containing clay | |
| CN103205570A (en) | Method for producing vanadium pentoxide and by-product manganese sulfate from by using coal vanadium ore and pyrolusite together | |
| CN109097565A (en) | A method of the high-efficiency cleaning Extraction of rare earth from ion adsorption type rare earth ore | |
| CN114318020B (en) | A treatment method for separating thallium from thallium-containing sulfide residue | |
| CN112522512B (en) | Method for preparing battery-grade cobalt sulfate by using organic cobalt slag of zinc smelting plant | |
| WO2012171481A1 (en) | Hydrometallurgical process for complete and comprehensive recovery with substantially no wastes and zero emissions | |
| CN113955775B (en) | Method for extracting lithium carbonate from lithium-rich clay by acid-base combined method | |
| CN103739005B (en) | Method for preparing thallous chloride using lead zinc ore smelting wastewater as raw material | |
| CN103773967A (en) | Method for recycling silver, copper and zinc from sintered ash in iron and steel plant | |
| CN118207426A (en) | Method for extracting lithium by composite roasting and leaching of clay type lithium ore | |
| CN105439192A (en) | Comprehensive utilization method for zinc oxide ore | |
| Liu et al. | A new process of extracting vanadium from stone coal | |
| CN113512652B (en) | Method for extracting gallium metal from coal-series solid waste | |
| CN103449483A (en) | Impurity removing method in process of preparing alumina from fly ash by utilizing acid method | |
| CN113293281A (en) | Method for leaching lithium from lepidolite | |
| CN109280776B (en) | A kind of method for recovering chromium in electroplating sludge by sub-molten salt method | |
| CN104911361B (en) | Method for enriching zinc oxide concentrate by wet treatment of zinc-containing dust in iron and steel plant | |
| CN116497236A (en) | Method for extracting lithium from phospholith-aluminum stone raw material |
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 |