CN114875250B - Method for purifying lithium from lithium-containing clay - Google Patents
Method for purifying lithium from lithium-containing clay Download PDFInfo
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- CN114875250B CN114875250B CN202210538781.4A CN202210538781A CN114875250B CN 114875250 B CN114875250 B CN 114875250B CN 202210538781 A CN202210538781 A CN 202210538781A CN 114875250 B CN114875250 B CN 114875250B
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B1/00—Preliminary treatment of ores or scrap
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- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
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Abstract
The invention relates to the technical field of metal smelting, and particularly provides a method for purifying lithium from lithium-containing clay, which comprises the following steps: activating lithium clay; acidizing and aluminum fixing are carried out on the activated lithium clay; and (3) carrying out solution leaching on the lithium clay subjected to the acidification treatment and the solid aluminum treatment to purify lithium. The lithium-containing clay has high aluminum and fluorine content and low lithium content, and the conventional roasting-acid leaching process has serious atmospheric fluorine pollution and high aluminum content of leaching liquid, so that the loss of impurity-removing lithium is large. According to the scheme of the invention, a mechanochemical-roasting-water leaching scheme is adopted, lithium-containing clay aluminum and fluorine are efficiently solidified, aluminum leaching and fluorine volatilization are reduced, the lithium leaching rate is more than 90%, the concentration of leached aluminum ions is less than 1g/L, the comprehensive recovery rate of lithium is more than 70%, the lithium carbonate product reaches the standard of battery-grade lithium carbonate, the purity of lithium carbonate is more than or equal to 99.5%, and lithium resources in the lithium-containing clay are effectively recovered.
Description
Technical Field
The invention relates to the technical field of metal smelting, in particular to a method for purifying lithium from lithium-containing clay.
Background
Lithium resources in nature can be generally classified into three types of brine type, hard rock type and clay type in salt lakes. Currently, the most utilized world-wide mining is brine type lithium ores and hard rock type lithium ores of salt lakes. Clay-type lithium ores are found later and are not developed and utilized on a large scale, but the distribution pattern and the practical requirement of the existing lithium resources make the lithium ores of the type highly valued. The lithium ore purifying process can be classified into a direct leaching method, an auxiliary agent roasting method and a chlorination and vulcanization method. The direct leaching method is a process of extraction by adding a leaching agent directly to an ore which has not been subjected to high-temperature roasting, as opposed to roasting leaching. Mainly comprises a water leaching method, a sulfuric acid leaching method and the like. For volcanic clay-type lithium ores, the more effective lithium extraction process mainly focuses on using auxiliary agents and ore samples for mixed roasting (or granulating roasting), and then leaching with water to obtain a lithium-containing solution. Common adjuvants include: hydroxides, carbonates, sulphates, chlorides, limestone, gypsum and other natural or industrial by-products. Sulfur chlorideBy chemical treatment, i.e. subjecting the sample to HCl or SO 2 And (3) roasting in the atmosphere for a period of time, and leaching the fully chlorinated or vulcanized clay lithium ore sample by water. Each leaching process has inherent defects, the leaching efficiency of the water leaching method is lower, the aluminum content of the leaching solution of the acid leaching method is high, the loss rate of impurity-removing lithium is high, the roasting temperature of the sulfate roasting method is high, the energy consumption is high, the corrosion of the chlorination and vulcanization method to equipment is serious, and the environmental protection pressure is high.
According to the data disclosed at present, the lithium element is basically in the solution, so that the separation is easier, but the brine type lithium resource of the salt lake has low abundance, higher treatment cost and mature process, the development cost is further reduced, the development potential is lower, and the development and utilization potential is further limited; the development and purification process and the reduction of the development cost of hard rock type and clay type lithium resources are increasingly focused due to high abundance and large reserves. Hard rock type lithium resources are widely used as a source which is widely developed at present, have a compact structure due to geological reasons, and have low impurity introduced during purification of lithium elements; however, hard rock type lithium resources have high requirements on ore veins, so that the ore veins which can be practically mined are limited and belong to non-sustainable resources, and adverse effects on the environment are difficult to avoid in ore vein mining. In contrast, clay-type lithium resources have been previously considered as a source of no development value due to their loose structure, high impurity dissolution rate and low recovery rate; however, clay-type lithium resources are always a treasure with huge reserves due to short vein formation time and less severe formation conditions. There is no engineering solution currently in operation for the extraction of lithium from lithium-containing clays, most of which are in the laboratory stage. The lithium-containing clay has high aluminum and fluorine content and low lithium content, and the conventional roasting-acid leaching process has serious atmospheric fluorine pollution and high aluminum content of leaching liquid, so that the loss of impurity-removing lithium is large, and the improvement of the lithium-containing clay extraction process is needed.
Disclosure of Invention
The invention aims to solve at least one technical problem in the background art, further reduce impurity introduction in the process of extracting lithium from lithium-containing clay, reduce pollution of toxic substances (such as fluorine) and further improve purity and yield of lithium.
To achieve the above object, the present invention provides a method for purifying lithium from a lithium-containing clay, comprising the steps of: activating the lithium-containing clay; acidizing and aluminum fixing are carried out on the activated lithium-containing clay; and (3) carrying out solution leaching on the lithium-containing clay after the acidification treatment and the solid aluminum treatment to purify lithium.
In one aspect of the invention, the agent for the activation treatment is a sulfate; the lithium-containing clay is volcanic clay type lithium ore, carbonate clay type lithium ore or Gu Daer lithium boron ore; the mass ratio of the sulfate to the lithium-containing clay is in the range of 0-0.5:1, a step of; the sulfate is one or more of sodium sulfate, potassium sulfate, sodium thiosulfate, potassium thiosulfate, calcium sulfate, ferrous sulfate and ferric sulfate.
In one aspect of the invention, the activation treatment is mechanochemical activation; the mechanochemical activation time is 10min-120min; the mechanochemical activation is achieved by a stirred mill, planetary mill, vibratory mill or roller mill.
In one aspect of the invention, the aluminum solidification treatment adopts one or more of calcium-containing ore, calcium-containing salt, calcium-containing inorganic alkali and calcium-containing inorganic oxide; the mass ratio of the reagent used in the solid aluminum treatment to the activated lithium-containing clay is in the range of 0.01-0.5:1, a step of; and, the reagent used in the aluminum fixation treatment is used as a fluorine fixation reagent for reducing fluorine elution.
In one aspect of the invention, the aluminum fixing treatment adopts one or more of calcium carbonate, calcite, limestone, calcium oxide and calcium hydroxide.
In one aspect of the present invention, the acidification treatment uses any one of concentrated sulfuric acid, citric acid and oxalic acid; the mass ratio of the reagent used in the acidification treatment to the activated lithium-containing clay is in the range of 0-1:1.
in one aspect of the invention, the acidification treatment and the aluminum solidification treatment simultaneously require heat treatment with the temperature of 300-1000 ℃ and the time of 10-480 min; the heat treatment is achieved by a tunnel kiln, an acidification roasting rotary kiln, a grate rotary kiln or a jacketed reaction kettle.
In one aspect of the invention, the leaching temperature of the solution for leaching and purifying lithium is 10-50 ℃, the leaching time is 30-480 min, and the solid ratio of the leaching solution is 1-10; the raw material liquid for extracting and purifying lithium by the solution is water or acid; the solution is leached and purified by a jacket reaction kettle, a stirring tank or a pressurizing reaction kettle.
In one aspect of the invention, the operation of solution leaching to purify lithium is: the method comprises the steps of leaching raw material liquid for extracting and purifying lithium by solution, performing first solid-liquid separation to obtain a leaching solution, circularly using the leaching solution for leaching lithium-containing clay after acidification treatment and solid-aluminum treatment, adding hydrogen peroxide and sodium hydroxide mixed solution into the leaching solution after the accumulated lithium concentration in the leaching solution is more than 10g/L, and performing first impurity removal and second solid-liquid separation; the impurities removed by the first impurity removal include aluminum and iron.
In one aspect of the present invention, sodium carbonate or potassium carbonate may be added to the separated liquid of the second solid-liquid separation after the second solid-liquid separation, and then precipitated, and the crude lithium carbonate may be prepared by the third solid-liquid separation.
In one aspect of the invention, the separation liquid of the third solid-liquid separation can be used for leaching and purifying lithium from the lithium-containing clay after the acidification treatment and the solid-aluminum treatment or recycling the lithium as a resource after water removal.
In one aspect of the invention, the crude lithium carbonate can be further washed by saturated lithium carbonate solution, added with carbon dioxide for treatment and then filtered and refined to obtain refined lithium carbonate solution
In one aspect of the invention, the refined lithium carbonate solution can be further subjected to secondary impurity removal by cationic resin and further water removal to prepare high-purity lithium carbonate; the secondary impurity removal impurity comprises: magnesium and calcium; the mass composition of the high-purity lithium carbonate meets the following conditions: li (Li) 2 CO 3 ≥99.5％。
Advantageous effects
According to the technical proposal of the invention, the dregs of the natural lithium-containing clay and the separated materials after lithium purification can be effectively processedThe lithium extraction is carried out in steps, the lithium in the lithium-containing clay is leached and recovered, so that the lithium content of the finally separated lithium-containing clay is obviously reduced, the high-efficiency utilization of mineral resources is ensured, the resources are effectively saved, the problems of more impurities, pollution of toxic substances (such as fluorine) and low lithium yield in the purification of the lithium-containing clay are solved, the source of lithium elements is further expanded, and the leaching rate of lithium in the lithium-containing clay of a lithium ore is ensured>Comprehensive recovery rate of 90% and lithium>80%, prepare Li 2 CO 3 In the product, li 2 CO 3 More than or equal to 99.5 percent, and lithium resources in the lithium-containing clay are effectively recycled:
1. the sulfate treatment is adopted to change the surface and crystal lattice of lithium-containing particles of the lithium-containing clay at the microscopic level, and the position of the crystal lattice containing lithium is replaced by cations in the sulfate to finish the transfer of lithium, so that the lithium is dispersed from an original more stable phase state to a less stable phase state (such as an ionic state), the further collection and separation are facilitated, and the reaction rate of the sulfate and the lithium in a stable state can be accelerated compared with a common uniform mixing high-temperature roasting process;
2. further, under the action of mechanochemical treatment equipment, the reaction efficiency of sulfate and lithium raw materials is improved, friction and collision at a microscopic level are favorable for crushing, destroying and refining lithium-containing substance particles, the specific surface area of the lithium-containing substance particles is increased, the reaction rate is further increased, and the yield of lithium elements is increased;
3. the addition of the solid aluminum reagent can effectively reduce the leaching rate of aluminum ions and the concentration of the aluminum ions in the leaching solution during leaching, thereby being beneficial to reducing the loss in the lithium extraction process and improving the comprehensive recovery rate of lithium;
4. the aluminum fixing reagent is added to play a role in fixing fluorine, reduce the volatilization rate of fluorine and reduce the emission of fluorine and the pollution to the atmosphere.
Drawings
FIG. 1 schematically shows a flow chart of a method for purifying lithium from a lithium-containing clay according to the invention;
FIG. 2 schematically shows a flow chart of a method for purifying lithium from a lithium-containing clay according to one embodiment of the invention;
FIG. 3 schematically shows a flow chart of a method for purifying lithium from a lithium-containing clay in example 1 according to the invention;
fig. 4 schematically shows a flow chart of a method for purifying lithium from a lithium-containing clay according to example 2 of the present invention.
Detailed Description
The present disclosure will now be discussed with reference to exemplary embodiments. It should be understood that the embodiments discussed are merely to enable those of ordinary skill in the art to better understand and thus practice the teachings of the present invention and do not imply any limitation on the scope of the invention.
As used herein, the term "comprising" and variants thereof are to be interpreted as meaning "including but not limited to" open-ended terms. The term "based on" is to be interpreted as "based at least in part on". The terms "one embodiment" and "an embodiment" are to be interpreted as "at least one embodiment.
FIG. 1 schematically shows a flow chart of a method for purifying lithium from a lithium-containing clay according to the invention; fig. 2 schematically shows a flow chart of a method for purifying lithium from a lithium-containing clay according to an embodiment of the invention. As shown in connection with fig. 1 and 2, the method for purifying lithium from a lithium-containing clay according to the present invention comprises the steps of:
a. uniformly mixing lithium-containing clay with a sulfate additive, and performing mechanochemical activation;
b. mixing the activated lithium-containing clay with acid, performing heat treatment on the mixed lithium-containing clay and the acid, and simultaneously performing aluminum solidification treatment in the heat treatment process;
c. carrying out solution leaching on the lithium-containing clay treated in the step b to purify lithium;
d. performing first solid-liquid separation after lithium purification to obtain leaching solution and leaching slag, recycling the leaching solution for leaching in the step c, adding hydrogen peroxide and sodium hydroxide into the leaching solution after lithium purification after lithium concentration in the leaching solution is more than 10g/L to precipitate aluminum and iron impurities, and performing first impurity removal; adding sodium carbonate or potassium carbonate into the separation liquid of the second solid-liquid separation after removing impurities of the first impurity removal through the second solid-liquid separation, and then obtaining crude lithium carbonate and lithium-precipitated residual liquid through the third solid-liquid separation, wherein the lithium-precipitated residual liquid is reused in the step c for leaching and purifying lithium or is reused by adopting evaporation and crystallization to obtain mixed sulfate;
e. washing the crude lithium carbonate by using a saturated lithium carbonate solution, pulping, introducing carbon dioxide for hydrogenation, removing insoluble carbonate, and filtering to obtain a refined lithium carbonate solution;
f. and deeply removing calcium and magnesium from the refined lithium carbonate solution through cationic resin, and roasting to obtain the battery-grade lithium carbonate.
In this embodiment, the mass ratio of sulfate additive to lithium-containing clay is in the range of 0 to 0.5:1, mechanochemical activation time is 10min-120min;
the acid in the step b is any one of concentrated sulfuric acid, citric acid and oxalic acid, and the mass ratio of the acid to the lithium-containing clay is 0-1:1; concentrated sulfuric acid with concentration of more than 95%, citric acid and oxalic acid as solid
The heat treatment temperature is 300-1000 ℃ and the heat treatment time is 20-480 min.
The mass ratio of the aluminum fixing reagent to the activated lithium-containing clay is in the range of 0.01-0.5:1.
The raw material liquid of the leaching agent is water or acid, the leaching temperature is 10-40 ℃, the leaching time is 30-480 min, and the solid ratio of the leaching agent is 1-10; the acid is 5% -50% sulfuric acid solution.
In this embodiment, the sulfate additive is one or a combination of several of sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, calcium sulfate, ferrous sulfate and ferric sulfate.
The aluminum fixing agent is one or a combination of more of calcium carbonate, calcite, limestone, calcium oxide and calcium hydroxide.
The lithium-containing clay is volcanic clay type lithium ore, carbonate clay type lithium ore or and Gu Daer lithium boron ore.
In this embodiment, mechanochemical activation of the first material is achieved by a stirred mill, planetary mill, vibratory mill, or roller mill;
the heat treatment is realized through a tunnel kiln, an acidification roasting rotary kiln, a grate rotary kiln or a jacketed reaction kettle;
water leaching or acid leaching is realized through a jacket reaction kettle, a stirring tank or a pressurizing reaction kettle;
the solid-liquid separation is realized by a plate-and-frame filter press, a precision filter or a belt filter.
According to the scheme, the advantages of the two processes of mechanical and chemical combined heat treatment are adopted, lithium extraction can be effectively carried out on the lithium-containing clay, the heat treatment roasting temperature of the lithium-containing clay is reduced, the leaching and recovery of lithium in the lithium-containing clay are carried out, the lithium content of the finally separated lithium-containing clay is obviously reduced, meanwhile, the content of impurity ions (such as fluorine and aluminum) in the leaching solution can be further reduced by adding a unique aluminum fixing and fluorine fixing process, the impurity ion content in the leaching solution is ensured to be low, the lithium loss in the leaching solution purifying process and environmental pollution are avoided, the efficient utilization of mineral resources is ensured, the resource is effectively saved, the lithium leaching rate of the lithium-containing clay is ensured to be more than 90%, the aluminum ion concentration of the leaching solution is less than 1g/L, the comprehensive recovery rate of lithium is more than 70%, the purity of lithium carbonate is more than or equal to 99.5%, and the lithium carbonate product reaches the battery grade lithium carbonate industry standard (Y/S582-2006), and the lithium resources in the lithium-containing clay are effectively recycled.
For ease of understanding, the present invention is exemplified by the following examples. It will be appreciated by those skilled in the art that the following examples are only preferred embodiments of the present invention, and are merely to aid in understanding the present invention, and thus should not be construed as limiting the scope of the present invention.
Test method
The method for testing fluorine element in lithium clay or lithium ore comprises the following steps: reference is made to GB/T15555.12-1995 method for determining ion-selective electrodes from fluoride in solid waste.
The method for testing fluorine element in the leaching solution comprises the following steps: GB/T5009.167-2003 reversed phase high performance liquid chromatography.
The method for testing the lithium element in the lithium clay or the lithium ore comprises the following steps: chemical analysis method of lithium ore, rubidium ore and cesium ore part 1: lithium determination GB/T17413.1-2010.
The method for testing the alumina in the lithium clay, the lithium ore or the leaching slag of the lithium ore comprises the following steps: GB T6730.56-2004 flame atomic absorption method for determining the aluminium content of iron ore.
The method for testing the concentration of aluminum ions in the leaching solution comprises the following steps: graphite furnace atomic absorption method.
The method for testing the lithium element in the leaching solution comprises the following steps: flame atomic absorption method.
Aluminum leaching rate = concentration of aluminum ions in leaching solution x leaching solution volume/(mass of lithium-containing raw material x aluminum content of lithium-containing raw material) x 100%; and when the leaching rate of the aluminum is that the concentration of lithium in the leaching solution is more than 10g/L, calculating according to the concentration of aluminum ions in the leaching solution.
Fluorine volatilization rate= (fluorine content of lithium-containing raw material-fluorine content of leached slag after treatment)/fluorine content of lithium-containing raw material x 100%; the fluorine content of the lithium-containing raw material and the fluorine content of the treated lithium-containing raw material are calculated by the dry weight of the dried lithium-containing raw material or the dry weight of the treated lithium-containing raw material.
Lithium leaching rate = concentration of lithium ions in leaching solution x leaching solution volume/(mass of lithium-containing raw material x lithium element content of lithium-containing raw material) x 100%.
The above-mentioned lithium-containing raw material is any one of the lithium clay or lithium ore disclosed in the present application, and the treatment mode of the lithium-containing raw material is any one of the methods disclosed in the present application for treating the lithium-containing raw material, recovering and collecting lithium or lithium compounds, unless otherwise specified.
Example 1
And comparing leaching rate of certain lithium-containing clay (volcanic clay type lithium ore) in Henan, certain lepidolite leaching slag in Jiangxi and spodumene in Sichuan with aluminium ion concentration of leaching liquid and fluorine content of leaching slag by adopting a conventional roasting-water leaching process. Heat treatment conditions: sodium sulfate addition amount is 20%, roasting temperature is 950 ℃, and water leaching temperature is 25 ℃. The dosage of sodium hydroxide and hydrogen peroxide is 10g/L, and water is selected as the leaching solution. Adopting the process flow shown in figure 3 to treat the lepidolite leaching slag of Jiangxi province and spodumene of Sichuan province as a control; meanwhile, a blank is set, the same Henan certain lithium-containing clay is adopted, the process flow shown in the figure 2 is adopted, the acidification treatment process is not included, and compared with the process flow shown in the figure 3, only the aluminum fixing reagent (calcium carbonate) treatment process is added; table 1 shows the raw material composition and specific parameters of the aluminum leaching rate, and table 2 shows the reagents and process conditions for the four experimental groups of this example:
TABLE 1
TABLE 2
Table 1 shows: under the same technological conditions, the leaching rate of lithium-containing clay aluminum is highest, and the concentration of aluminum ions in the leaching solution is highest. This is because the internal crystal structure of the soft structure of the lithium-containing clay is not compact, and the impurity elements are more easily leached out; and the lepidolite leaching slag, spodumene and other lithium ores are subjected to high pressure and even high temperature and high pressure combined action during geological formation, so that the crystal structure and the texture are more compact, and the advantage of low leaching rate of impurity elements (especially aluminum) is achieved. And excessive aluminum impurities can generate a large amount of amorphous aluminum hydroxide in subsequent impurity removal, and a large amount of lithium is lost due to adsorption and fixation of lithium.
In this example, lepidolite, spodumene, and lithium-containing clays were treated using the methods provided in fig. 2 or fig. 3, and the test results are shown in table 3 below:
TABLE 3 Table 3
In the embodiment, compared with lepidolite leaching residues and spodumene, fluorine in the lithium-containing clay is seriously volatilized, so that certain pollution is caused to air, the lithium leaching rate is higher, but the comprehensive recovery rate of lithium is lower due to higher concentration of aluminum ions in the leaching solution and the concentration of aluminum ions in the lithium-precipitating residual liquid; the aluminum-fixing reagent calcium carbonate is added in the blank, the aluminum ion content in the leaching solution and the lithium-precipitating residual solution is obviously reduced, and the fluorine volatilization rate is also obviously reduced.
Example 2
Further, in order to verify the influence of mechanochemical activation treatment on the lithium comprehensive recovery rate of the lithium-containing clay, experimental group 1 and experimental group 2 were set up: experiment group 1 was treated using the method of fig. 2, and the treatment process did not include acidification treatment and aluminum fixing reagent addition; experiment group 2 was treated using the method of fig. 4. The difference is that experiment 1 was subjected to mechanochemical activation for 5min, while experiment 2 was not subjected to mechanochemical activation, the remaining conditions being the same.
As shown in table 4, the experimental group 1 and the experimental group 2 adopt the same certain lithium-containing clay (carbonate clay type lithium ore) in Henan, the dosage of sodium hydroxide and hydrogen peroxide is 5g/L, the leaching solution adopts 5% dilute sulfuric acid, as shown in table 5, and the heat treatment is carried out under the same conditions: sodium sulfate addition amount is 20%, roasting temperature is 950 ℃, and water leaching temperature is 25 ℃.
TABLE 4 Table 4
TABLE 5
In this example, the lithium-containing clay provided by the present invention was treated by the method of fig. 2 and 4, and the test results are shown in table 6 below: after the experiment group 1 adopts mechanochemical activation treatment, the lithium leaching rate and the comprehensive lithium recovery rate are both obviously improved compared with the experiment group 2 which does not adopt mechanochemical activation treatment, and meanwhile, the concentration of aluminum ions in the lithium-depositing residual liquid is not obviously changed, which indicates that the introduction of mechanochemical activation treatment is beneficial to improving the reaction efficiency of sulfate and lithium raw materials and does not bring adverse effects to the comprehensive lithium recovery rate.
TABLE 6
Example 3
Certain Guizhou lithium-containing clay contains lithium oxide (Gu Daer lithium boron ore, the content of lithium oxide is 0.45%, the content of alumina is 19%, the content of fluorine is 1.5%, aluminum phase bauxite) and adopts the process flow shown in figure 2, specific parameters are shown in the following table 7, citric acid is selected as an acidification treatment, calcium oxide is selected as an aluminum fixing reagent, the dosage of sodium hydroxide and hydrogen peroxide is 3g/L, 25% dilute sulfuric acid by mass fraction is selected as a leaching solution, and the same process is adopted to treat certain spodumene leaching residues (the content of lithium oxide is 0.5%, the content of alumina is 27%, the content of fluorine is 0.5%, aluminum phase aluminosilicate) of Sichuan, certain lithium iron mica (the content of lithium oxide is 2.5%, the content of alumina is 31%, the content of fluorine is 3.5% and aluminum phase iron lithium mica) as a control:
TABLE 7
In this example, the method for purifying lithium by using the lithium-containing clay for lithium ore provided by the invention is used for treating spodumene leaching residue, petalite and lithium-containing clay, and the test results are shown in the following table 8:
TABLE 8
From the above, the method for purifying lithium from the lithium-containing clay provided by the invention is used for treating the lithium-containing clay, wherein the lithium leaching rate of the lithium-containing clay is more than 90%, the concentration of aluminum ions in a lithium-deposition residual liquid is less than 1g/L, the comprehensive recovery rate of lithium is more than 84%, the fluorine volatilization rate is less than or equal to 6%, lithium resources in the lithium-containing clay are effectively recovered, and the volatilization of fluorine elements is effectively inhibited.
Example 4
Certain Yunnan lithium-containing clay contains lithium oxide (lithium oxide content 0.54%, aluminum oxide content 25%, fluorine content 2.1%, aluminum phase bauxite and mica) (carbonate clay type lithium ore), oxalic acid is selected for acidification treatment, sodium hydroxide and hydrogen peroxide are used for acidification treatment, the leaching solution is prepared from dilute sulfuric acid with mass fraction of 50%, calcium hydroxide is selected for aluminum fixing reagent, specific parameters are shown in the following table 9, and the same process is adopted for treating certain lithium iron mica leaching residues (lithium oxide content 0.48%, aluminum oxide content 25%, fluorine content 3.5%, aluminum phase aluminosilicate) and certain African phospholithium (lithium oxide content 4.5%, aluminum oxide content 24%, fluorine content 0.8% and aluminum phase phospholithium aluminum) for comparison, wherein specific results are shown in the following table 10:
TABLE 9
In this example, the above method for purifying lithium from lithium-bearing clay for lithium ore provided by the present invention was used to treat lithium-bearing clay for lithium mica, and the test results are shown in table 6 below:
table 10
From the above, the method for purifying lithium from the lithium-containing clay provided by the invention is used for treating the lithium-containing clay, wherein the lithium leaching rate of the lithium-containing clay is more than 90%, the concentration of aluminum ions in a lithium-deposition residual liquid is less than 1g/L, the comprehensive recovery rate of lithium is more than 84%, the fluorine volatilization rate is less than or equal to 5%, lithium resources in the lithium-containing clay are effectively recovered, and the volatilization of fluorine elements is effectively inhibited.
Example 5
Certain lithium-containing clay (Gu Daer lithium boron ore) contains 0.3% of lithium oxide, the process flow shown in fig. 2 is adopted, the acidizing treatment adopts concentrated sulfuric acid with the mass fraction of 95%, the dosage of sodium hydroxide and hydrogen peroxide is 10g/L, the leaching solution adopts water, and the specific parameters are shown in the following table 11:
TABLE 11
In this example, the method for purifying lithium by using the above-mentioned lithium-containing clay for lithium ore provided by the present invention is used for treating petalite-containing clay, and the test results are shown in table 12 below:
table 12
From the above, the method for purifying lithium from the lithium-containing clay provided by the invention is used for treating the lithium-containing clay, wherein the lithium leaching rate of the lithium-containing clay is more than 90%, the concentration of aluminum ions in the lithium-precipitating residual liquid is less than 1g/L, the comprehensive recovery rate of lithium is more than 70%, and lithium resources in the lithium-containing clay are effectively recovered.
Finally, it is noted that the above-mentioned preferred embodiments are only intended to illustrate rather than limit the invention, and that, although the invention has been described in detail by means of the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. A method for purifying lithium from a lithium-containing clay, comprising the steps of: activating the lithium-containing clay; acidizing and aluminum fixing are carried out on the activated lithium-containing clay; carrying out solution leaching on the lithium-containing clay after the acidification treatment and the solid aluminum treatment to purify lithium;
the activating treatment reagent is sulfate; the lithium-containing clay is volcanic clay type lithium ore, carbonate clay type lithium ore or Gu Daer lithium boron ore; the mass ratio of the sulfate to the lithium-containing clay is in the range of 0.25-0.5:1, a step of; the sulfate is one or more of sodium sulfate, potassium sulfate, sodium thiosulfate, potassium thiosulfate, calcium sulfate, ferrous sulfate and ferric sulfate;
the activation treatment is mechanochemical activation; the mechanochemical activation time is 10min-120min; the mechanochemical activation is achieved by a stirring mill, a planetary mill, a vibratory mill or a roller mill;
the aluminum fixing treatment adopts one or more of calcium-containing ore, calcium salt, calcium-containing inorganic alkali and calcium-containing inorganic oxide; the mass ratio of the reagent used in the solid aluminum treatment to the activated lithium-containing clay is in the range of 0.01-0.5:1, a step of; and, the reagent used in the aluminum fixation treatment is used as a fluorine fixation reagent for reducing fluorine dissolution;
the acidification treatment uses any one of concentrated sulfuric acid, citric acid and oxalic acid; the mass ratio of the reagent used in the acidification treatment to the activated lithium-containing clay is in the range of 0.1-1:1, a step of;
the acidification treatment and the aluminum solidification treatment simultaneously require heat treatment with the temperature of 300-1000 ℃ and the time of 10-480 min; the heat treatment is achieved by a tunnel kiln, an acidification roasting rotary kiln, a grate rotary kiln or a jacketed reaction kettle.
2. The method of claim 1, wherein the aluminum fixing treatment is one or more of calcium carbonate, calcite, limestone, calcium oxide, and calcium hydroxide.
3. The method according to claim 1, wherein the leaching temperature of the solution leaching purified lithium is 10 ℃ to 50 ℃ and the leaching time is 30min to 480min, and the solid ratio of the leaching solution is 1 to 10; the raw material liquid for extracting and purifying lithium by the solution is water or acid; the solution is leached and purified by a jacket reaction kettle, a stirring tank or a pressurizing reaction kettle.
4. A method according to claim 3, wherein the operation of solution leaching to purify lithium is: the method comprises the steps of leaching raw material liquid for purifying lithium by solution leaching and carrying out first solid-liquid separation to obtain a leaching solution, circularly using the leaching solution for leaching lithium-containing clay after acidification treatment and solid-aluminum treatment, adding hydrogen peroxide and sodium hydroxide mixed liquid into the leaching solution for carrying out first impurity removal and second solid-liquid separation after the accumulated lithium concentration of the leaching solution is more than 10 g/L; the impurities removed by the first impurity removal include aluminum and iron.
5. The method according to claim 4, wherein sodium carbonate or potassium carbonate is added to the separated liquid of the second solid-liquid separation after the second solid-liquid separation, and then the obtained mixture is precipitated and subjected to the third solid-liquid separation to prepare crude lithium carbonate.
6. The method according to claim 5, wherein the separated liquid of the third solid-liquid separation can be used for leaching and purifying lithium from the lithium-containing clay after the acidification treatment and the solid-aluminum treatment or can be recycled as a resource after water removal.
7. The method according to claim 5, wherein the crude lithium carbonate is further purified by washing with a saturated lithium carbonate solution, adding carbon dioxide, treating, and filtering.
8. The method of claim 7, wherein the refined lithium carbonate solution is further subjected to a second purification by a cationic resin to produce high purity lithium carbonate; the second impurity removal impurity comprises: magnesium and calcium; the mass composition of the high-purity lithium carbonate meets the following conditions: li2CO3 is more than or equal to 99.5 percent.
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| CN115786732A (en) * | 2022-11-11 | 2023-03-14 | 湖北金泉新材料有限公司 | Method for extracting lithium resource from clay type lithium ore |
| CN115976337B (en) * | 2022-12-19 | 2024-08-23 | 福州大学 | Method for extracting lithium ions from clay type lithium ores with extremely low lithium grade by utilizing ion replacement |
| CN116002736B (en) * | 2022-12-29 | 2024-06-11 | 四川顺应锂材料科技有限公司 | Method for preparing aluminum hydroxide by pressure leaching and separating aluminum and lithium from clay lithium ore |
| CN116179873A (en) * | 2023-02-24 | 2023-05-30 | 广东邦普循环科技有限公司 | Method for recovering lithium from lithium clay |
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