CN114875250A - Method for purifying lithium from lithium-containing clay - Google Patents
Method for purifying lithium from lithium-containing clay Download PDFInfo
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- 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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- C22B1/00—Preliminary treatment of ores or scrap
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- 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 the lithium clay; performing acidification treatment and aluminum fixation treatment on the activated lithium clay; and (4) carrying out solution leaching on the lithium clay after the acidification treatment and the aluminum fixation treatment to purify the lithium. The lithium-containing clay has high aluminum and fluorine contents and low lithium contents, the atmospheric fluorine pollution is serious in the conventional roasting-acid leaching process, and the impurity-removed lithium loss is large due to the high aluminum content of a leaching solution. According to the scheme of the invention, a mechanochemistry-roasting-water leaching scheme is adopted, the lithium-containing clay is efficiently solidified by aluminum and fluorine, the leaching of aluminum and the volatilization of fluorine are reduced, the leaching rate of lithium is more than 90%, the concentration of aluminum ions in a leaching solution is less than 1g/L, the comprehensive recovery rate of lithium is more than 70%, a 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
Natural lithium resources can be generally divided into salt lakesBrine type, hard rock type and clay type. Currently, salt lake brine type lithium ores and hard rock type lithium ores are most widely exploited and utilized worldwide. The clay type lithium ore is discovered later and is not developed and utilized on a large scale, but the distribution pattern and the practical requirements of lithium resources exist, so that the clay type lithium ore is highly valued. The process for purifying lithium from lithium ore can be summarized as a direct leaching method, an auxiliary agent roasting method and a chlorination and vulcanization method. The direct leaching method is relative to roasting leaching and mainly refers to an extraction process which is carried out by directly adding a leaching agent to ore which is not roasted at a high temperature. Mainly comprises a water leaching method, a sulfuric acid leaching method and the like. For volcanic clay type lithium ore, the effective lithium extraction process mainly focuses on the mixed roasting (or granulation roasting) of the auxiliary agent and the ore sample, and then the lithium-containing solution is obtained by adopting water immersion. Commonly used adjuvants include: hydroxides, carbonates, sulfates, chlorides, and natural materials such as limestone and gypsum or industrial byproducts. The chlorination-vulcanization method is to put the sample in HCl or SO 2 Roasting in the atmosphere for a period of time, and then carrying out water leaching on the fully chloridized or vulcanized clay lithium ore sample. Each leaching process has inherent defects, namely low leaching efficiency of a water leaching method, high aluminum content of leaching liquid of an acid leaching method, high impurity-removed lithium loss rate, high roasting temperature of a sulfate roasting method, high energy consumption, serious corrosion of a chlorination and vulcanization method on equipment and high environmental protection pressure.
According to the currently disclosed data, the salt lake brine type lithium resource is easy to separate because the lithium element is basically in the solution, but the salt lake brine type lithium resource is low in abundance, high in treatment cost and mature in process, so that the development cost is further reduced, the potential is low, and the potential for further development and utilization is limited; because of high abundance and large reserves, the hard rock type and clay type lithium resources have become the focus of increasing attention on how to improve the development and purification process and reduce the development cost. The hard rock type lithium resource is taken as a widely developed source at present, has a compact structure due to geological reasons, has less impurity introduced when purifying lithium element, and has been widely applied; however, because the hard rock type lithium resource has higher requirements on the vein, the actually available vein is limited, and belongs to unsustainable resources, and the adverse effect on the environment is difficult to avoid in the vein exploitation. The difference is that the clay type lithium resource is considered as a source without development value before due to loose structure, high impurity dissolution rate and low recovery rate; however, the clay type lithium resource is always treasure with huge reserves due to short formation time of the mineral vein and less harsh formation conditions. Currently, no engineering technical scheme has been operated for extracting lithium from lithium-containing clay, and most of the technology is in a laboratory stage. The lithium-containing clay has high aluminum and fluorine contents and low lithium content, the conventional roasting-acid leaching process has serious atmospheric fluorine pollution, and the leaching solution has high aluminum content, so that the loss of impurity-removed lithium is large, and the improvement of the lithium-containing clay lithium extraction process is urgently needed.
Disclosure of Invention
The invention aims to solve at least one technical problem in the background art, further reduce the introduction of impurities in the lithium-containing clay lithium extraction process, reduce the pollution of toxic substances (such as fluorine) and further improve the purity and yield of lithium.
In order to achieve the above object, the present invention provides a method for purifying lithium from lithium-containing clay, comprising the following steps: activating the lithium-containing clay; acidifying and fixing aluminum on the activated lithium-containing clay; and (3) carrying out solution leaching on the lithium-containing clay after the acidification treatment and the aluminum fixation treatment to purify the lithium.
In one aspect of the invention, the activating agent is a sulfate; the lithium-containing clay is volcanic clay type lithium ore, carbonate clay type lithium ore or Jadar lithium boron ore; the mass ratio of the sulfate to the lithium-containing clay ranges from 0 to 0.5: 1; the sulfate is one or more of sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, 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-120 min; the mechanochemical activation is effected by means of a stirred mill, a planetary mill, a vibrating mill or a roller mill.
In one aspect of the invention, the aluminous treatment employs one or more of a calcium-containing ore, a calcium-containing salt, a calcium-containing inorganic base, a calcium-containing inorganic oxide; the mass ratio of the reagent used in the aluminum fixation treatment to the activated lithium-containing clay ranges from 0.01 to 0.5: 1; and the reagent used for the solid aluminum treatment is used as a fluorine-fixing reagent for reducing the elution of fluorine.
In one aspect of the invention, the aluminium fixation treatment employs one or more of calcium carbonate, calcite, limestone, calcium oxide, calcium hydroxide.
In one aspect of the present invention, the acidification treatment uses any one of concentrated sulfuric acid, citric acid, oxalic acid; the mass ratio of the reagent used for the acidification treatment to the activated lithium-containing clay ranges from 0 to 1: 1.
in one aspect of the invention, the acidification treatment and the aluminum fixation treatment simultaneously require heat treatment at a temperature of 300 ℃ to 1000 ℃ for 10min to 480 min; the heat treatment is realized 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 for leaching and purifying lithium by the solution 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 the lithium by the solution leaching is water or acid; the lithium is extracted and purified by the solution through a jacket reaction kettle, a stirring tank or a pressurized reaction kettle.
In one aspect of the present invention, the operation of solution leaching to purify lithium is: after the raw material solution for extracting and purifying lithium by solution leaching is leached, 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, and after the concentration of lithium accumulated in the leaching solution is more than 10g/L, adding a mixed solution of hydrogen peroxide and sodium hydroxide into the leaching solution to perform first impurity removal and second solid-liquid separation; the impurities removed by the first impurity removal comprise aluminum and iron.
In one aspect of the present invention, after the second solid-liquid separation, sodium carbonate or potassium carbonate may be added to the separated liquid of the second solid-liquid separation, followed by precipitation and a third solid-liquid separation to prepare crude lithium carbonate.
In one aspect of the invention, the separation liquid of the third solid-liquid separation can be used for leaching and purifying lithium or removing water from the lithium-containing clay after acidification treatment and solid-aluminum treatment and then recycling the lithium-containing clay as a resource.
In one aspect of the present invention, the crude lithium carbonate may be further washed with a saturated lithium carbonate solution, treated with carbon dioxide, filtered and refined to obtain a refined lithium carbonate solution
In one aspect of the invention, the refined lithium carbonate solution may be further subjected to secondary impurity removal by a cationic resin and further water removal to prepare high-purity lithium carbonate; the secondary impurity removal impurities comprise: magnesium and calcium; the quality composition of the high-purity lithium carbonate meets the following conditions: li 2 CO 3 ≥99.5％。
Advantageous effects
According to the technical scheme of the invention, the natural lithium-containing clay and the dregs of the separated materials after lithium purification can be effectively subjected to further lithium extraction, and 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 lithium-containing clay purification are solved, the lithium element source is further expanded, and the leaching rate of the lithium in the lithium-containing clay of the lithium mine is ensured>90 percent and comprehensive lithium recovery rate>80% to obtain Li 2 CO 3 In the product, Li 2 CO 3 Not less than 99.5%, and effectively recycling the lithium resource in the lithium-containing clay:
1. the sulfate treatment is adopted, so that the surface and the crystal lattice of lithium-containing substance particles of the lithium-containing clay change on a microscopic level, the crystal lattice position containing lithium is replaced by cations in the sulfate to complete the transfer of lithium, and the lithium is dispersed from an original more stable phase state to a less stable phase state (such as an ionic state), thereby being beneficial to further collection and separation, and the more common uniform mixing high-temperature roasting process can accelerate the reaction rate of the sulfate and the lithium in the stable state;
2. furthermore, under the action of mechanical-chemical treatment equipment, the method is beneficial to improving the reaction efficiency of the sulfate and the lithium raw material, and is beneficial to crushing, destroying and refining the lithium-containing substance particles through friction and collision on a microscopic layer, so that the specific surface area of the lithium-containing substance particles is increased, the reaction rate is further increased, and the lithium element yield is increased;
3. the aluminum fixing reagent is added, so that the leaching rate of aluminum ions in leaching and the concentration of the aluminum ions in the leaching liquid can be effectively reduced, the loss in the lithium extraction process can be reduced, and the comprehensive recovery rate of lithium can be improved;
4. the solid aluminum reagent is added to play a role in fluorine fixation, so that the volatilization rate of fluorine is reduced, and the emission of fluorine and the pollution to the atmosphere are reduced.
Drawings
FIG. 1 schematically shows a flow diagram of a method for purifying lithium from a lithium-containing clay according to the invention;
FIG. 2 schematically shows a flow diagram of a method for purifying lithium from a lithium-containing clay according to one embodiment of the invention;
FIG. 3 is a flow chart schematically showing a method for purifying lithium from a lithium-containing clay according to example 1 of the present 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 content of the invention will now be discussed with reference to exemplary embodiments. It should be understood that the embodiments discussed are only for the purpose of enabling a person of ordinary skill in the art to better understand and thus implement the contents of the present invention, and do not imply any limitation on the scope of the present invention.
As used herein, the term "include" and its variants are to be read as open-ended terms meaning "including, but not limited to. The term "based on" is to be read as "based, at least in part, on". The terms "one embodiment" and "an embodiment" are to be read as "at least one embodiment".
FIG. 1 schematically shows a flow diagram of a method for purifying lithium from a lithium-containing clay according to the invention; fig. 2 schematically shows a flow diagram of a method for purifying lithium from a lithium-containing clay according to an embodiment of the present invention. Referring to fig. 1 and 2, a method for purifying lithium from a lithium-containing clay according to the present invention includes the steps of:
a. mixing lithium-containing clay and sulfate additive uniformly, and carrying out mechanochemical activation;
b. mixing the activated lithium-containing clay with acid, carrying out heat treatment on the mixed lithium-containing clay and the acid, and carrying out aluminum fixation treatment during the heat treatment process;
c. b, 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 leachate and leaching residues, wherein the leachate is recycled for leaching in the step c, and hydrogen peroxide and sodium hydroxide are added into the leachate after lithium purification after the concentration of lithium in the leachate is more than 10g/L to precipitate aluminum and iron impurities for first impurity removal; after impurities removed in the first time are removed through second solid-liquid separation, sodium carbonate or potassium carbonate is added into separation liquid of the second solid-liquid separation, then crude lithium carbonate and lithium deposition residual liquid are obtained through third solid-liquid separation, and the lithium deposition residual liquid is recycled for leaching purified lithium in the step c or mixed sulfate recycling is obtained through evaporative crystallization;
e. washing the crude lithium carbonate by using a saturated lithium carbonate solution, then regulating the size, introducing carbon dioxide for hydrogenation, removing insoluble carbonate, and filtering to obtain a refined lithium carbonate solution;
f. and (3) deeply removing calcium and magnesium from the refined lithium carbonate solution through cationic resin, and then roasting to obtain battery-grade lithium carbonate.
In this embodiment, the mass ratio of the sulfate additive to the lithium-containing clay ranges from 0 to 0.5:1, mechanochemical activation for 10min-120 min;
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; the concentrated sulfuric acid is more than 95%, and the citric acid and the oxalic acid are 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 0.01-0.5: 1.
Selecting water or acid as raw material liquid of the leaching solution, wherein the leaching temperature is 10-40 ℃, the leaching time is 30-480 min, and the solid ratio of the leaching solution is 1-10; the acid is a 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 Jadar lithium boron ore.
In the embodiment, mechanochemical activation of the first material is achieved by a stirring mill, a planetary mill, a vibration mill or a roller mill;
the heat treatment is realized through a tunnel kiln, an acidification roasting rotary kiln, a chain grate rotary kiln or a jacket reaction kettle;
water leaching or acid leaching is realized through a jacket reaction kettle, a stirring tank or a pressurized 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 of the invention, the advantages of the mechanochemistry and the heat treatment are combined, the lithium extraction can be effectively carried out on the lithium-containing clay, the roasting temperature of the heat treatment of the lithium-containing clay is reduced, the leaching and recovery of the 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 the unique aluminum-fixing and fluorine-fixing processes, the low content of the impurity ions in the leaching solution is ensured, the excessive lithium loss and the environmental pollution in the purification process of the leaching solution are avoided, the high-efficiency utilization of mineral resources is ensured, the resources are effectively saved, the lithium-containing clay lithium leaching rate is ensured to be more than 90%, the aluminum ion concentration of the leaching solution is less than 1g/L, the comprehensive lithium recovery rate is more than 70%, the lithium carbonate purity is more than or equal to 99.5%, and the lithium carbonate product reaches the battery-grade lithium carbonate industrial standard (Y/S582-),2006), the lithium resource in the lithium-containing clay is effectively recycled.
For ease of understanding, the present invention is illustrated 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, are only for the purpose of facilitating understanding of the present invention, and thus should not be taken as limiting the scope of the present invention.
Test method
The method for testing fluorine elements in lithium clay or lithium ore comprises the following steps: refer to GB/T15555.12-1995 fluoride determination ion selective electrode method in solid waste.
The method for testing the fluorine element in the leaching solution comprises the following steps: GB/T5009.167-2003 reversed phase high performance liquid chromatography.
The method for testing lithium elements in lithium clay or lithium ore comprises the following steps: chemical analysis method for lithium ore, rubidium ore and cesium ore part 1: and measuring the amount of the lithium by GB/T17413.1-2010.
The method for testing the aluminum oxide in the leached residues of the lithium clay, the lithium ore or 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 leachate comprises the following steps: graphite furnace atomic absorption method.
The method for testing lithium element in the leaching solution comprises the following steps: flame atomic absorption method.
The leaching rate of aluminum is equal to the concentration of aluminum ions in the leaching solution multiplied by the volume of the leaching solution/(mass of lithium-containing raw material multiplied by the content of aluminum in the lithium-containing raw material multiplied by 100 percent; 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 leaching residue 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 processed lithium-containing raw material are both calculated by the dry weight of the dried lithium-containing raw material or the processed lithium-containing raw material.
The leaching rate of lithium is lithium ion concentration in the leaching solution multiplied by the volume of the leaching solution/(mass of lithium-containing raw material multiplied by lithium element content of lithium-containing raw material) multiplied by 100%.
The lithium-containing raw material is any one of the lithium clay or the lithium ore disclosed in the present application, and if not specifically stated, the lithium-containing raw material processing mode is any one of the methods for processing the lithium-containing raw material, recovering and collecting lithium or lithium compounds disclosed in the present application.
Example 1
The leaching rate of some lithium-containing clay (volcanic clay type lithium ore) in Henan, some lepidolite leaching residue in Jiangxi and some spodumene in Sichuan, the aluminum ion concentration of the leaching solution and the fluorine content of the leaching residue are compared by adopting a conventional roasting-water leaching process. And (3) heat treatment conditions: the addition amount of sodium sulfate is 20 percent, the roasting temperature is 950 ℃, and the water immersion temperature is 25 ℃. The dosage of sodium hydroxide and hydrogen peroxide is 10g/L, and the leaching solution is selected from water. The process flow shown in FIG. 3 is adopted to treat some lepidolite leaching residues in Jiangxi and some spodumene in Sichuan as a reference; meanwhile, a blank control is set, the same certain lithium-containing clay in Henan is adopted, the process flow shown in figure 2 is adopted, the acidification treatment process is not included, and only the treatment process of an aluminum fixing reagent (calcium carbonate) is added compared with the process flow shown in figure 3; table 1 shows specific parameters of raw material composition and aluminum leaching rate, and table 2 shows reagents and process conditions for four experimental groups of this example:
TABLE 1
TABLE 2
Table 1 shows: under the same process conditions, the leaching rate of the lithium-containing clay and aluminum is highest, and the concentration of aluminum ions in the leaching solution is highest. This is because the crystal structure inside the lithium-containing clay soft structure is not compact, and impurity elements are more easily leached out; and the lepidolite leaching residue and the spodumene and other lithium ores are subjected to combined action of high pressure, even high temperature and high pressure during geological formation, so that the crystal structure and the texture are more compact, and the method has the advantage of low leaching rate of impurity elements (particularly aluminum). And too high aluminum impurities can generate a large amount of amorphous aluminum hydroxide in subsequent impurity removal, and can adsorb and fix lithium to cause a large amount of lithium loss.
In this example, lepidolite, spodumene, lithium-containing clay were treated as provided in either figure 2 or figure 3 and the results are shown in table 3 below:
TABLE 3
Compared with lepidolite leaching residues and spodumene, fluorine in the lithium-containing clay is seriously volatilized, certain pollution is caused to air, the lithium leaching rate is higher, but the comprehensive recovery rate of lithium is lower due to higher aluminum ion concentration in the leaching solution and higher aluminum ion concentration in a lithium-precipitating residual solution; and the blank is added with solid aluminum reagent calcium carbonate, so that the aluminum ion content in the leaching solution and the lithium precipitation residual liquid is obviously reduced, and the fluorine volatilization rate is also obviously reduced.
Example 2
Further, in order to verify the influence of the mechanochemical activation treatment mode on the comprehensive lithium recovery rate of the lithium-containing clay, an experimental group 1 and an experimental group 2 are arranged: the experimental group 1 is treated by the method shown in the attached figure 2, and the treatment process does not comprise acidification treatment and aluminum fixing reagent adding process; experimental group 2 was treated using the method of figure 4. The difference is that the experimental group 1 is activated for 5min by mechanochemical activation, while the experimental group 2 is not activated by mechanochemical activation, and the rest conditions are the same.
As shown in table 4, the same lithium-containing clay (carbonate clay type lithium ore) in south of Henan was used in the experimental group 1 and the experimental group 2, the amounts of sodium hydroxide and hydrogen peroxide were both 5g/L, and the leaching solution was treated with 5% dilute sulfuric acid under the same conditions as shown in table 5: the addition amount of sodium sulfate is 20 percent, the roasting temperature is 950 ℃, and the water immersion temperature is 25 ℃.
TABLE 4
TABLE 5
In this example, the lithium-containing clay provided by the present invention was treated by the methods shown in FIGS. 2 and 4, and the test results are shown in Table 6 below: after the experiment group 1 is subjected to mechanochemical activation treatment, the lithium leaching rate and the comprehensive lithium recovery rate are both remarkably improved compared with the experiment group 2 which is not subjected to mechanochemical activation treatment, and meanwhile, the concentration of aluminum ions in the lithium precipitating residual liquid is not remarkably changed, which shows that the introduction of mechanochemical activation treatment is beneficial to improving the reaction efficiency of sulfate and lithium raw materials, and the comprehensive lithium recovery rate is not adversely affected.
TABLE 6
Example 3
Certain Guizhou lithium-containing clay contains lithium oxide (jiadaler Limonite, the content of lithium oxide is 0.45%, the content of aluminum oxide is 19%, the content of fluorine is 1.5%, and an aluminum-phase bauxite), the process flow shown in FIG. 2 is adopted, specific parameters are shown in the following table 7, citric acid is selected for acidification, calcium oxide is selected as an aluminum fixing reagent, the using amounts of sodium hydroxide and hydrogen peroxide are both 3g/L, dilute sulfuric acid with the mass fraction of 25% is selected for a leaching solution, and the same process is adopted to treat some Liminopsite leaching residues in Sichuan (the content of lithium oxide is 0.5%, the content of aluminum oxide is 27%, the content of fluorine is 0.5%, and an aluminum-phase aluminosilicate), some LiFeiMusco in Yichun (the content of lithium oxide is 2.5%, the content of aluminum oxide is 31%, the content of fluorine is 3.5%, and the aluminum-phase LiFeiMusco) is used as a reference:
TABLE 7
In this embodiment, the method for purifying lithium from lithium-containing clay in lithium ore provided by the present invention is used to treat the spodumene leaching residue, lepidolite, and lithium-containing clay, and the test results are shown in table 8 below:
TABLE 8
From the above, when the method for purifying lithium from lithium-containing clay provided by the invention is used for treating the lithium-containing clay, the leaching rate of lithium in the lithium-containing clay is greater than 90%, the concentration of aluminum ions in lithium precipitation raffinate is less than 1g/L, the comprehensive recovery rate of lithium is greater 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 (the content of lithium oxide is 0.54 percent, the content of aluminum oxide is 25 percent, the content of fluorine is 2.1 percent, aluminum phase bauxite and mica) (carbonate clay type lithium ore), the process flow shown in FIG. 2 is adopted, oxalic acid is selected for acidification, the using amounts of sodium hydroxide and hydrogen peroxide are both 5g/L, dilute sulfuric acid with the mass fraction of 50 percent is selected for a leaching solution, and calcium hydroxide is selected for an aluminum fixing reagent, and specific parameters are shown in the following Table 9, the leaching residue of certain LiFeOOH mica of Jiujiang (the content of lithium oxide is 0.48 percent, the content of aluminum oxide is 25 percent, the content of fluorine is 3.5 percent, the aluminum phase aluminosilicate), certain LiFeOOH of Africa (the content of lithium oxide is 4.5 percent, the content of aluminum oxide is 24 percent, the content of fluorine is 0.8 percent, and the aluminum phase LiOOH) are treated by the same process as a reference, and specific results are shown in the following Table 10:
TABLE 9
In this example, the lepidolite lithium-containing clay was treated by the method for purifying lithium from lithium-containing clay of lithium ore provided by the present invention, and the test results are shown in table 6 below:
watch 10
From the above, when the method for purifying lithium from lithium-containing clay provided by the invention is used for treating the lithium-containing clay, the leaching rate of lithium in the lithium-containing clay is greater than 90%, the concentration of aluminum ions in lithium precipitation raffinate is less than 1g/L, the comprehensive recovery rate of lithium is greater 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
0.3% of lithium oxide in certain lithium-containing clay (Galaxal Limonite), adopting the process flow shown in FIG. 2, selecting concentrated sulfuric acid with the mass fraction of 95% for acidification treatment, wherein the using amount of sodium hydroxide and hydrogen peroxide is 10g/L, and selecting water for leaching liquid, wherein the specific parameters are shown in the following table 11:
TABLE 11
In this example, the method for purifying lithium from lithium-containing clay of lithium ore provided by the present invention is used to treat the lithium-containing petalite clay, and the test results are shown in table 12 below:
TABLE 12
From the above, when the method for purifying lithium from lithium-containing clay provided by the invention is used for treating lithium-containing clay, the leaching rate of lithium from the lithium-containing clay is greater than 90%, the concentration of aluminum ions in lithium precipitation raffinate is less than 1g/L, the comprehensive recovery rate of lithium is greater than 70%, and lithium resources in the lithium-containing clay are effectively recovered.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (13)
1. The method for purifying lithium from lithium-containing clay is characterized by comprising the following steps: activating the lithium-containing clay; acidifying and fixing aluminum on the activated lithium-containing clay; and (3) carrying out solution leaching on the lithium-containing clay after the acidification treatment and the aluminum fixation treatment to purify the lithium.
2. The method according to claim 1, wherein the activating agent is a sulfate; the lithium-containing clay is volcanic clay type lithium ore, carbonate clay type lithium ore or Jadar lithium boron ore; the mass ratio of the sulfate to the lithium-containing clay ranges from 0 to 0.5: 1; the sulfate is one or more of sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, calcium sulfate, ferrous sulfate and ferric sulfate.
3. The method of claim 1, wherein the activation treatment is mechanochemical activation; the mechanochemical activation time is 10min-120 min; the mechanochemical activation is effected by means of a stirred mill, a planetary mill, a vibrating mill or a roller mill.
4. The method of claim 1, wherein the aluminous fixation treatment employs one or more of a calcium-containing ore, a calcium-containing salt, a calcium-containing inorganic base, a calcium-containing inorganic oxide; the mass ratio of the reagent used in the aluminum fixation treatment to the activated lithium-containing clay ranges from 0.01 to 0.5: 1; and the reagent used for the solid aluminum treatment is used as a fluorine-fixing reagent for reducing the elution of fluorine.
5. The method according to claim 4, wherein the aluminium fixation treatment employs one or more of calcium carbonate, calcite, limestone, calcium oxide, calcium hydroxide.
6. The method according to claim 1, wherein the acidification treatment uses any one of concentrated sulfuric acid, citric acid, oxalic acid; the mass ratio of the reagent used for the acidification treatment to the activated lithium-containing clay ranges from 0 to 1: 1.
7. the method according to claim 1, characterized in that the acidification treatment and the aluminium fixation treatment simultaneously require a heat treatment at a temperature of 300 ℃ to 1000 ℃ for a time of 10min to 480 min; the heat treatment is realized by a tunnel kiln, an acidification roasting rotary kiln, a grate rotary kiln or a jacketed reaction kettle.
8. The method according to claim 1, wherein the leaching temperature for purifying lithium by solution leaching 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 the lithium by the solution leaching is water or acid; the lithium is extracted and purified by the solution through a jacket reaction kettle, a stirring tank or a pressurized reaction kettle.
9. The method of claim 8, wherein the solution leaching to purify lithium is performed by: leaching the raw material solution obtained by leaching and purifying lithium with the solution, and performing first solid-liquid separation to obtain a leachate, wherein the leachate is circularly used for leaching lithium-containing clay subjected to acidification treatment and solid-aluminum treatment, and after the accumulated lithium concentration of the leachate is more than 10g/L, adding a mixed solution of hydrogen peroxide and sodium hydroxide into the leachate to perform first impurity removal and second solid-liquid separation; the impurities removed by the first impurity removal comprise aluminum and iron.
10. The method according to claim 9, wherein after the second solid-liquid separation, sodium carbonate or potassium carbonate can be added into the separation liquid of the second solid-liquid separation, and then the precipitation and third solid-liquid separation are carried out to prepare crude lithium carbonate.
11. The method as claimed in claim 10, wherein the separated liquid of the third solid-liquid separation can be used for the extraction and purification of lithium from the lithium-containing clay after acidification and aluminum fixation or for the recovery as resources after water removal.
12. The method according to claim 10, wherein the crude lithium carbonate may be further washed with a saturated lithium carbonate solution, treated with carbon dioxide, and then filtered and refined to obtain a refined lithium carbonate solution.
13. The method of claim 12, wherein the refined lithium carbonate solution is further removed by a second pass through a cationic resinPreparing high-purity lithium carbonate; the second impurity removal impurities comprise: magnesium and calcium; the quality composition of the high-purity lithium carbonate meets the following conditions: li 2 CO 3 ≥99.5％。
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