CN112941339B - Method for preparing metallic lithium by taking alkali leaching solution of aluminum-lithium co-existing resource as raw material - Google Patents

Method for preparing metallic lithium by taking alkali leaching solution of aluminum-lithium co-existing resource as raw material Download PDF

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CN112941339B
CN112941339B CN202110128206.2A CN202110128206A CN112941339B CN 112941339 B CN112941339 B CN 112941339B CN 202110128206 A CN202110128206 A CN 202110128206A CN 112941339 B CN112941339 B CN 112941339B
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lithium
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aluminum
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leaching
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CN112941339A (en
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田勇攀
赵�卓
肖松文
陈雯雯
王成成
张福元
徐亮
华中胜
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Anhui University of Technology AHUT
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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a method for preparing metal lithium by taking an aluminum-lithium symbiotic resource alkali leaching solution as a raw material, belonging to the technical field of lithium ion recovery. The method mainly comprises the following processes: adsorbing lithium ions in the lithium-containing sodium aluminate solution by adopting an adsorbent; carrying out solid-liquid separation, and then carrying out resolution and concentration; after concentration, adding a precipitator to generate aluminum lithium composite hydroxide precipitate; mixing and roasting the lithium-containing precipitate and an additive to prepare a lithium-rich clinker; and mixing the concentrated lithium salt solution and the lithium-rich clinker for briquetting, drying the briquetted material, and then carrying out vacuum aluminothermic reduction to prepare the metallic lithium. Wherein, the sodium aluminate solution prepared by leaching the reduced calcium aluminate slag and the calcium carbonate can be respectively used as a precipitator and an additive to return to the process, thereby realizing the recycling of the materials. The method has the advantages of wide raw material source, simple process, environmental protection and low cost, does not influence the aluminum extraction process of the lithium-aluminum symbiotic resource, and is suitable for industrial popularization.

Description

Method for preparing metal lithium by taking aluminum-lithium symbiotic resource alkali leaching solution as raw material
Technical Field
The invention belongs to the technical field of lithium ion recovery, and particularly relates to a method for preparing metal lithium by taking an aluminum-lithium co-existing resource alkali leaching solution as a raw material.
Background
In recent years, lithium metal has been called "energy metal" because its use in aerospace, nuclear power generation, and energy batteries has been increasing. The production method of the metallic lithium generally comprises a molten salt electrolysis method and a metallothermic reduction method, but at the present stage, more than 90% of the metallic lithium is generally prepared by a lithium chloride-potassium chloride molten salt electrolysis method.
The lithium source for preparing the metal lithium by the molten salt electrolysis method is anhydrous lithium chloride, and the preparation method of the lithium chloride comprises the step of reacting hydrochloric acid with lithium hydroxide or lithium carbonate with chlorine gas. For example, patent CN101573296a (published as 11/4/2009) discloses "a method for preparing lithium metal". The process adopts chlorine gas lithium chloride carbonate and anhydrous lithium chloride as raw materials to prepare the metallic lithium by a molten salt electrolysis method. For another example, patent CN101760759a (published in 2010, 6/month, 30/day) also uses lithium chloride-potassium chloride molten salt electrolysis to prepare lithium metal, but adopts an automatic lithium discharging method. The process for preparing the metal lithium by the molten salt electrolysis method has the following defects that (1) the electrolysis method consumes expensive lithium chloride and has high requirement on the purity of the lithium chloride; (2) The process involving chlorine in the generating process is more, and the requirement on the corrosion resistance of equipment is high; (3) The whole process comprises the procedures of preparing lithium chloride, electrolyzing lithium chloride and the like, and has long flow and high cost.
The vacuum thermal reduction method includes a carbothermic reduction method and a metallothermic reduction method, wherein the metallothermic reduction method further includes a silicothermic reduction method, an ferrothermic reduction method and an aluminothermic reduction method. The carbothermic method for producing the metal lithium is easy to be secondarily oxidized, has low lithium yield, is not suitable for operation and is difficult to industrially popularize. The iron heat reduction method and the silicon heat reduction method for preparing the metal lithium cannot realize the recycling of materials, cannot be integrated with the production process of the high-alumina fly ash and the alumina, and have low material utilization rate. The aluminothermic vacuum reduction process may be integrated with the alumina production process, e.g., fedorov et al at a pressure of 1.2X 10 -8 atm, reducing lithium aluminate and metallic aluminum at 1200 ℃ to obtain metallic lithium, wherein the reduction rate is 95%. Kroll et Al add CaO during aluminothermic reduction, caO and Al during reaction 2 O 3 The combination makes the metal lithium more volatile, and the pressure is 1.3 multiplied by 10 -6 atm, reacting for 15h at the temperature of about 900 ℃, and the reduction rate of lithium metal is more than 80%. For another example, in patent CN102560148a (application publication date: 7/12/2012), "a method for refining lithium by vacuum aluminothermic reduction", the process takes lithium hydroxide and lithium carbonate as raw materials containing lithium, and adds alumina, aluminum hydroxide and calcium oxide to prepare Li after roasting 5 AlO 4 The lithium is smelted by adopting a vacuum aluminothermic reduction mode after the roasting material and the aluminum powder are mixed and pelletized, but the process needs to prepare lithium hydroxide and lithium carbonate firstly, so the cost is higher.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects of multiple working procedures, long process flow, high production cost, incapability of realizing material recycling and the like when the traditional process is adopted for preparing the lithium metal, and provides a method for preparing the lithium metal by taking the alkali leaching solution of the aluminum-lithium co-existing resource as a raw material. By adopting the technical scheme of the invention, the problems can be effectively solved, the lithium extraction process is optimized, the preparation cost is relatively low, and the material utilization rate can be further improved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a method for preparing metal lithium by taking an aluminum-lithium symbiotic resource alkali leaching solution as a raw material, which comprises the following steps:
(1) Preparing an adsorbent;
(2) Adsorption and filtration: adsorbing lithium ions in the lithium-containing sodium aluminate solution by using the adsorbent obtained in the step (1), and filtering;
(3) Desorption, concentration and precipitation: firstly, desorbing the adsorbent which finishes adsorption in the step (2) by adopting a desorbent to obtain a desorption solution; then concentrating the desorption solution; finally, adding a precipitator into a part of concentrated solution to prepare a lithium-aluminum alkaline compound, and keeping the other part of concentrated solution for later use;
(4) Roasting: mixing the lithium-aluminum alkaline compound obtained in the step (3) with an additive, and roasting to prepare a lithium-rich clinker;
(5) Briquetting and drying the slurry: mixing the lithium-rich clinker obtained in the step (4) with the concentrated solution concentrated in the step (3), briquetting and drying;
(6) Vacuum aluminothermic reduction: crushing the mixed material mass obtained in the step (5), fully mixing with aluminum powder, and carrying out aluminothermic reduction to obtain metal lithium;
(7) Leaching: crushing and leaching the calcium aluminate slag generated after aluminothermic reduction, and returning the obtained calcium carbonate serving as a roasting additive to the step (4) for cyclic utilization; and (4) returning the obtained sodium aluminate solution as a precipitator to the step (3) for recycling.
Furthermore, in the step (1), the prepared adsorbent is an LDH adsorbing material.
Furthermore, the preparation method of the LDH adsorbing material comprises the following steps: preparing a sodium aluminate solution with the concentration of 20-170g/L of alumina and the molar ratio of sodium oxide to alumina of 1.5-1.8, adding a LiOH solution into the sodium aluminate solution, controlling the concentration of Li ions to be 20-100ppm, reacting at 0-90 ℃ for 1d-10d, carrying out vacuum filtration, washing with water, and drying at 60-90 ℃ to obtain the adsorbing material.
Furthermore, in the step (2), the adsorption temperature is controlled to be 10-90 ℃, the adsorption time is 30min-48h, and the stirring speed is 200-300r/min; during filtering, a vacuum filter is adopted for solid-liquid separation.
Furthermore, in the step (3), during desorption, the desorption temperature is controlled to be 10-90 ℃, the desorption time is 30-48h, and the pH value of the desorption solution is 7-14; when in concentration, the concentration of the obtained LiOH concentrated solution is controlled to be 1-50g/L.
Furthermore, in the step (4), the roasting temperature is controlled to be 750-1000 ℃, and the sintering time is 0.5-2h; in the step (5), the radius of the obtained pellets is controlled to be 10-30mm, and the water content is controlled to be 5% -20%; the temperature range for drying the pellets is 50-90 ℃.
Furthermore, when aluminothermic reduction is carried out in the step (6), the molar ratio of the added metal aluminum to the lithium in the lithium-rich clinker is 0.3-0.4, the pressure is less than 20Pa, the reduction temperature is 750-1000 ℃, and the reduction time is 0.5-2h.
Furthermore, in the step (7), a sodium carbonate solution is adopted for leaching, and vacuum filtration is adopted for solid-liquid separation.
Furthermore, in the step (7), the calcium aluminate slag is ground to be less than 150 mu m, the leaching temperature is controlled to be 50-100 ℃, and Na is contained in the sodium carbonate solution 2 The concentration of O is controlled to be 80-150g/L, and the leaching time is 30-60min.
Further, the desorbent is distilled water, HCl and HNO 3 、H 2 SO 4 (ii) a The precipitating agent is preferably sodium aluminate solution; the roasting additive adopts calcium-containing salts.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The method for preparing the metallic lithium by taking the alkali leaching solution of the aluminum-lithium co-production resource as the raw material comprises the processes of adsorption, desorption, concentration, precipitation, roasting, slurry briquetting, vacuum aluminothermic reduction and leaching, and can effectively shorten the flow of extracting lithium from the alkali leaching solution of the aluminum-lithium co-production resource (bauxite, high-alumina fly ash, carbonate clay type lithium resource and the like) by optimally designing the process operation steps, so that the process is relatively simple and the production cost is obviously reduced. Meanwhile, through the optimization of the process, the cyclic utilization of resources can be realized, the cyclic utilization rate of materials is further improved, and the economic benefit is high.
(2) According to the method for preparing the metallic lithium by taking the alkali leaching solution of the aluminum-lithium co-production resource as the raw material, the lithium-rich clinker obtained after roasting treatment and the concentrated solution obtained in the previous step are mixed, agglomerated and dried, and then are subjected to aluminothermic vacuum thermal reduction to prepare the metallic lithium, so that the Li/Al ratio in the vacuum aluminothermic reduction process can be effectively improved. Meanwhile, the Li/Al ratio can be regulated and controlled in real time according to the concentration of the prepared slurry lithium salt, the difficulty that the Li/Al ratio is difficult to regulate in the traditional process for preparing the metal lithium by adopting vacuum aluminothermic reduction is solved, the vacuum thermit reduction rate is greatly improved, and the production cost is reduced.
(3) According to the method for preparing the metallic lithium by taking the alkali leaching solution of the aluminum-lithium co-generation resource as the raw material, the preparation process of the metallic lithium is adjusted, so that the metallic lithium is directly prepared from the alkali leaching solution, the calcium aluminate slag which is a byproduct in the preparation of the metallic lithium is leached by adopting a circulation process, the obtained sodium aluminate solution is used as a precipitator, and the calcium carbonate is used as a roasting additive for recycling, so that the utilization rate of the material is effectively improved.
(4) According to the method for preparing the metal lithium by taking the aluminum-lithium co-production resource alkali leaching solution as the raw material, the LDH adsorption material is prepared to adsorb the aluminum-lithium co-production resource alkali leaching solution (mainly a sodium aluminate solution), and the lithium ions in the alkali leaching solution are preliminarily enriched, so that the separation effect of the lithium ions and other metal ions is favorably improved, and the recovery rate of the lithium ions is improved. Meanwhile, the preparation process of the adsorption material is optimized, specifically, the lithium ion adsorbent aluminum lithium alkaline compound is prepared by adopting a lithium-containing sodium aluminate solution (namely an alkaline leaching solution) self-precipitation mode, and technological parameters in the preparation process are strictly controlled, so that the adsorption effect of the adsorption material is effectively ensured.
(5) The method for preparing the metal lithium by taking the alkali leaching solution of the aluminum-lithium co-production resource as the raw material optimizes the temperature, the treatment duration and the like of the whole process, has the advantages of short flow, low cost, simple operation, small corrosion to equipment and the like, and is wide in raw material source and environment-friendly. Meanwhile, the preparation process of the metal lithium can be fused with an aluminum-lithium symbiotic resource aluminum extraction process, so that the comprehensive recovery of the aluminum lithium is easy to realize.
Drawings
FIG. 1 is a process flow diagram of a method for preparing metallic lithium by using an alkali leaching solution of an aluminum-lithium co-generation resource as a raw material according to the invention;
FIG. 2 is a XRD analysis result chart of the aluminum adsorbent prepared by the self-precipitation method in example 1;
FIG. 3 is a diagram showing the XRD analysis results of the solid-phase precipitation of lithium aluminum hydroxide prepared in example 1.
Detailed Description
The existing traditional preparation methods of metal lithium mainly fall into two categories, one is a molten salt electrolysis method; one type is the metallothermic reduction process. Among them, when the molten salt electrolysis method is used to prepare the metal lithium, the raw material with high price is usually consumed, and taking lithium chloride as an example, the following defects exist when the raw material is used to prepare the metal lithium: (1) the purity requirement on lithium chloride is high; (2) The chlorine gas is designed in more processes in the generation process, and the requirement on the corrosion resistance of equipment is high; (3) The whole process comprises the procedures of preparing lithium chloride, electrolyzing lithium chloride and the like, and has long flow and high cost. The metallothermic reduction method is adopted, and the common carbothermic, ferrothermic and silicothermic reduction methods are adopted to prepare the metallic lithium, and the defects of the metallolithium are as follows: (1) The carbon thermal reduction method is adopted to produce the metal lithium, so that the metal lithium is easy to be secondarily oxidized, the yield of the lithium is low, the operation is not suitable, and the industrial popularization is difficult; (2) The method for preparing the metallic lithium by adopting the ferrothermal reduction method (can be seen in Chinese patent with the publication number of CN 102382991A) and the silicothermal reduction method (can be seen in Chinese patent with the publication number of CN 1162022A) cannot realize the recycling of materials and can not be fused with the production process of the high-alumina fly ash and the production process of the alumina.
The invention provides a method for preparing metal lithium by taking an aluminum-lithium symbiotic resource alkali leaching solution as a raw material, which can effectively overcome the defects and shortcomings of the traditional process for preparing the metal lithium by optimizing the process operation steps, can obviously shorten the preparation flow, particularly the flow for extracting lithium from the aluminum-lithium symbiotic resource (bauxite, high-alumina fly ash, carbonate clay type lithium resource and the like) alkali leaching solution, has relatively simple working procedures, obviously reduces the production cost and is environment-friendly. Meanwhile, by optimizing the process, the cyclic utilization of resources can be effectively realized, the cyclic utilization rate of materials is further improved, and the economic benefit is high. The preparation method comprises the following steps:
(1) Preparation of the adsorbent
The invention adopts a self-precipitation method to prepare an aluminum LDH adsorbing material, and the specific preparation method comprises the following steps: firstly, preparing a sodium aluminate solution with the concentration of alumina of 20-170g/L and the molar ratio of sodium oxide to alumina of 1.5-1.8, adding LiOH solution into the sodium aluminate solution, controlling the concentration of Li ions to be 20-100ppm, reacting the mixed solution at 0-90 ℃ for 1d-10d, filtering in vacuum to obtain an aluminum LDH adsorbing material, washing with water, and drying at 60-90 ℃ to obtain the adsorbing material. According to the invention, the LDH adsorption material is prepared to adsorb the alkali leaching solution (mainly sodium aluminate solution) which is a resource of aluminum and lithium symbiosis, and the lithium ions in the alkali leaching solution are preliminarily enriched, so that the separation effect of the lithium ions and other metal ions is improved, and the recovery rate of the lithium ions is improved. Meanwhile, the preparation method is optimally designed, and technological parameters in the preparation process are strictly controlled, so that the adsorption effect can be effectively ensured, the operation process is simple, and the cost is low.
(2) Adsorbing and filtering
Adsorbing lithium ions in the lithium-containing sodium aluminate solution by using the adsorbent obtained in the step (1), and stirring, wherein the adsorption temperature is controlled to be 10-90 ℃, the adsorption time is 30min-48h, and the stirring speed is 200-300r/min; and after adsorption, filtering by using a vacuum filter to realize solid-liquid separation.
(3) Desorbing, concentrating, and precipitating
Firstly, desorbing the adsorbent which is adsorbed in the step (2) by adopting a desorption agent, wherein the desorption solution can adopt distilled water, HCl and HNO 3 、H 2 SO 4 And (3) when desorbing the desorption agent, controlling the desorption temperature to be 10-90 ℃, the desorption time to be 30-48h and the pH value of the desorption solution to be 7-14 to finally obtain the desorption solution. Then concentrating the desorption solution, and concentrating the LiOH solution, wherein the concentration of the LiOH solution is 1-50g/L. And finally, adding a precipitator sodium aluminate solution into one part of the concentrated solution to prepare a lithium-aluminum alkaline compound, and keeping the other part of the concentrated solution for later use. Upon precipitation, the main chemical reaction occurs as follows:
Li + +2Al(OH) 4 - +2H 2 O＝LiOH·2Al(OH) 3 ·2H 2 O+OH -
(4) Roasting
Mixing the obtained lithium-aluminum alkaline compound in step (3) with additive, sintering at 750-1000 deg.C for 0.5-2 hr, wherein the additive can be other calcium-containing salts such as calcium oxide, calcium carbonate, calcium hydroxide, etc., wherein CaO/Al 2 O 3 The molar ratio of the raw materials is 1-2, the lithium-rich clinker is prepared by roasting, and part of characteristic reactions are as follows:
LiOH·2Al(OH) 3 ·2H 2 O→LiAlO 2 +LiAl 5 O 8
CaCO 3 →CaO
(5) Briquetting and drying the slurry
And (4) mixing the lithium-rich clinker obtained in the step (4) with the concentrated solution concentrated in the step (3), briquetting and drying. Additives can be used or not used in the pelletizing process, the types of the additives comprise polyvinyl alcohol, silicic acid or cellulose and the like, the radius of the obtained pellets is controlled to be 10-30mm, and the water content is controlled to be 5-20%; the temperature range for drying the pellets is 50-90 ℃.
(6) Vacuum aluminothermic reduction
Crushing the mixed material mass obtained in the step (5), fully mixing with aluminum powder, and carrying out aluminothermic reduction to obtain metal lithium; when aluminothermic reduction is carried out, the molar ratio of the added metallic aluminum to lithium in the lithium-rich clinker is 0.3-0.4, the pressure is less than 20Pa, the reduction temperature is 750-1000 ℃, the reduction time is 0.5-2h, the generated lithium vapor is cooled and crystallized to form metallic lithium, and the main chemical reaction formula of the process is as follows:
3LiAlO 2 +2CaO+Al＝3Li+2(CaO·Al 2 O 3 )
21LiAlO 2 +24CaO+7Al＝21Li+2(12CaO·7Al 2 O 3 )
3LiAl 5 O 8 +8CaO+Al＝3Li+8(CaO·Al 2 O 3 )
21LiAl 5 O 8 +96CaO+7Al＝21Li+8(12CaO·7Al 2 O 3 )
(7) Leaching out
And crushing the calcium aluminate slag generated after aluminothermic reduction, leaching by using a sodium carbonate solution, and performing vacuum filtration for solid-liquid separation. Wherein, before leaching, the calcium aluminate slag is ground to be below 150 μm, the leaching temperature is controlled to be 50-100 ℃, and Na in the sodium carbonate solution is used 2 The concentration of O is controlled to be 80-150g/L, and the leaching time is 30-60min. Calcium carbonate obtained by leaching is used as a roasting additive and enters the step (4) for recycling; the obtained sodium aluminate solution can be used as a precipitator and recycled in the step (3). By adopting a circulation process, the by-product generated in the process of preparing the metallic lithium is preparedThe material, calcium aluminate slag, is leached, so that the utilization rate of the material is effectively improved.
It should be noted that, in the conventional process for preparing lithium metal by vacuum aluminothermic reduction, the Li/Al ratio is up to 1-5, which is difficult to improve. The invention prepares the metallic lithium by optimally designing the whole process flow, particularly mixing and briquetting the lithium-rich clinker obtained after roasting treatment and the concentrated solution obtained in the previous step, drying the mixture, and then carrying out aluminothermic vacuum thermal reduction, wherein the Li/Al ratio can be regulated according to the concentration of the prepared slurry lithium salt, so that the Li/Al ratio in the vacuum aluminothermic reduction process can be effectively controlled, and the Li/Al ratio can reach about 10 according to the addition amount of the slurry and the briquetting and drying conditions, and the Li/Al ratio has improved space, thereby greatly improving the vacuum thermal reduction rate, effectively solving the difficulty that the Li/Al ratio is difficult to regulate in the traditional process for preparing the metallic lithium by adopting vacuum aluminothermic reduction, and reducing the production cost. In addition, the method expands the lithium extraction resources into aluminum-lithium symbiotic resources (bauxite, high-alumina fly ash, carbonate clay type lithium resources and the like), has wide raw material sources, simple process, environmental friendliness and low cost, does not influence the aluminum extraction process of the lithium-aluminum symbiotic resources, is easy to realize the comprehensive recovery of aluminum and lithium, and is suitable for industrial popularization.
The invention is further described with reference to specific examples.
Example 1
As shown in fig. 1, the method for preparing lithium metal by using an alkali leaching solution of an aluminum-lithium co-occurring resource as a raw material according to this embodiment includes the following steps:
(1) Preparation of the adsorbent
The aluminum LDH adsorbing material is prepared by a self-precipitation method, and the specific preparation method comprises the following steps: firstly, preparing a sodium aluminate solution with the concentration of alumina of 100g/L and the molar ratio of sodium oxide to alumina of 1.6, adding a LiOH solution into the sodium aluminate solution, controlling the concentration of Li ions to be 30ppm, reacting the mixed solution at 25 ℃ for 5 days, filtering in vacuum to obtain an aluminum LDH adsorbing material, washing with water, and drying at 70 ℃ to obtain the adsorbing material.
XRD characterization was performed on the prepared adsorbent, and the results are shown in FIG. 1.
(2) Adsorbing and filtering
Adsorbing lithium ions in the lithium-containing sodium aluminate solution by using the adsorbent obtained in the step (1), and stirring, wherein the adsorption temperature is controlled to be 60 ℃, the adsorption time is 36 hours, and the stirring speed is 250r/min; and after adsorption, filtering by using a vacuum filter to realize solid-liquid separation.
(3) Desorbing, concentrating, and precipitating
Firstly, desorbing the adsorbent which is adsorbed in the step (2) by using a desorbent, wherein the desorbent can be distilled water, and during desorption, the desorption temperature is controlled to be 60 ℃, the desorption time is controlled to be 40h, and the pH value of the desorbent is 8, so that the desorbent is finally obtained. Then, the desorption solution was concentrated to obtain a concentrated LiOH solution having a concentration of 30g/L. And finally, adding a precipitator sodium aluminate solution into one part of the concentrated solution to prepare a lithium-aluminum alkaline compound, and keeping the other part of the concentrated solution for later use.
XRD characterization was performed on the prepared lithium aluminum basic complex (lithium aluminum hydroxide) solid phase precipitate, and the result is shown in FIG. 2.
(4) Roasting
Mixing the obtained lithium-aluminum alkaline compound in step (3) with additive, and sintering at 850 deg.C for 1.2 hr, wherein the additive can be other calcium-containing salts such as calcium oxide, calcium carbonate, and calcium hydroxide, wherein CaO/Al 2 O 3 The molar ratio of (1.5) and roasting to prepare the lithium-rich clinker.
(5) Briquetting and drying the slurry
And (4) mixing the lithium-rich clinker obtained in the step (4) with the concentrated solution concentrated in the step (3), briquetting and drying. Controlling the radius of the obtained pellets to be 20mm and the water content to be 15 percent; the temperature interval for drying the pellets is 75 ℃.
(6) Vacuum aluminothermic reduction
Crushing the mixed material mass obtained in the step (5), fully mixing with aluminum powder, and carrying out aluminothermic reduction to obtain metal lithium; when aluminothermic reduction is carried out, the molar ratio of the added metallic aluminum to the lithium in the lithium-rich clinker is 0.35, the pressure is less than 20Pa, the reduction temperature is 850 ℃, the reduction time is 1.5h, and the generated lithium vapor is cooled and crystallized to form the metallic lithium.
(7) Zxfoom
And crushing the calcium aluminate slag generated after aluminothermic reduction, leaching by using a sodium carbonate solution, and performing vacuum filtration for solid-liquid separation. Wherein before leaching, the calcium aluminate slag is ground to be less than 150 μm, the leaching temperature is controlled to be 60 ℃, and Na in the sodium carbonate solution is used 2 The concentration of O is controlled to be 90g/L, and the leaching time is 40min. Calcium carbonate obtained by leaching is used as a roasting additive and enters the step (4) for recycling; the obtained sodium aluminate solution can be used as a precipitator and recycled in the step (3).
Example 2
As shown in fig. 1, the method for preparing lithium metal by using an alkali leaching solution of an aluminum-lithium co-occurring resource as a raw material according to this embodiment includes the following steps:
(1) Preparation of the adsorbent
The aluminum LDH adsorbing material is prepared by a self-precipitation method, and the specific preparation method comprises the following steps: firstly, preparing a sodium aluminate solution with the concentration of alumina of 120g/L and the molar ratio of sodium oxide to alumina of 1.7, adding a LiOH solution into the solution, controlling the concentration of Li ions to be 40ppm, reacting the mixed solution at 35 ℃ for 8 days, filtering in vacuum to obtain an aluminum LDH adsorbing material, washing with water, and drying at 90 ℃ to obtain the adsorbing material.
XRD characterization was performed on the prepared adsorbent, and the result was substantially the same as in example 1.
(2) Adsorbing and filtering
Adsorbing lithium ions in the lithium-containing sodium aluminate solution by using the adsorbent obtained in the step (1), and stirring, wherein the adsorption temperature is controlled to be 50 ℃, the adsorption time is 24 hours, and the stirring speed is 200r/min; and after adsorption, filtering by using a vacuum filter to realize solid-liquid separation.
(3) Desorbing, concentrating, and precipitating
Firstly, desorbing the adsorbent which is completely adsorbed in the step (2) by using a desorption agent, wherein the desorption liquid can be H 2 SO 4 And during desorption, controlling the desorption temperature to be 50 ℃, the desorption time to be 35h, and the pH value of the desorption liquid to be 7 to finally obtain the desorption liquid. Then, the desorption solution was concentrated to obtain a concentrated LiOH solution having a concentration of 45g/L. Finally, a precipitate is added to a portion of the concentratePreparing sodium aluminate solution to obtain the lithium-aluminum alkaline compound, and preparing the other part of concentrated solution for later use.
XRD characterization was performed on the prepared lithium aluminum basic complex (lithium aluminum hydroxide) solid phase precipitate, and the result was substantially the same as in example 1.
(4) Roasting
Mixing the obtained lithium-aluminum alkaline compound in step (3) with additive, and sintering at 750 deg.C for 0.5 hr, wherein the additive can be other calcium-containing salts such as calcium oxide, calcium carbonate, and calcium hydroxide, wherein CaO/Al 2 O 3 The molar ratio of (1.6) and roasting to prepare the lithium-rich clinker.
(5) Briquetting and drying the slurry
Mixing the lithium-rich clinker obtained in the step (4) and the concentrated solution concentrated in the step (3), briquetting and drying, wherein the radius of the obtained pellet is controlled to be 10mm, and the water content is controlled to be 5%; the temperature interval for drying the pellets is 90 ℃.
(6) Vacuum aluminothermic reduction
Crushing the mixed material mass obtained in the step (5), fully mixing with aluminum powder, and carrying out aluminothermic reduction to obtain metal lithium; when aluminothermic reduction is carried out, the molar ratio of the added metallic aluminum to the lithium in the lithium-rich clinker is 0.3, the pressure is less than 20Pa, the reduction temperature is 750 ℃, the reduction time is 2 hours, and the generated lithium vapor is cooled and crystallized to form metallic lithium.
(7) Leaching out
And crushing the calcium aluminate slag generated after aluminothermic reduction, leaching by using a sodium carbonate solution, and performing vacuum filtration for solid-liquid separation. Wherein, before leaching, the calcium aluminate slag is ground to be below 150 μm, the leaching temperature is controlled to be 50 ℃, and Na is contained in the sodium carbonate solution 2 The O concentration is controlled to be 80g/L, and the leaching time is 35min. Calcium carbonate obtained by leaching is used as a roasting additive and enters the step (4) for recycling; the obtained sodium aluminate solution can be used as a precipitator and recycled in the step (3).
Example 3
As shown in fig. 1, the method for preparing lithium metal by using an alkali leaching solution of an aluminum-lithium co-occurring resource as a raw material according to this embodiment includes the following steps:
(1) Preparation of the adsorbent
The aluminum LDH adsorbing material is prepared by a self-precipitation method, and the specific preparation method comprises the following steps: firstly, preparing a sodium aluminate solution with the alumina concentration of 40g/L and the molar ratio of sodium oxide to alumina of 1.5, adding a LiOH solution into the sodium aluminate solution, controlling the concentration of Li ions at 100ppm, reacting the mixed solution at 90 ℃ for 1d, filtering in vacuum to obtain an aluminum LDH adsorbing material, washing with water, and drying at 60 ℃ to obtain the adsorbing material.
XRD characterization was performed on the prepared adsorbent, and the result was substantially the same as in example 1.
(2) Adsorbing and filtering
Adsorbing lithium ions in the lithium-containing sodium aluminate solution by using the adsorbent obtained in the step (1), and stirring, wherein the adsorption temperature is controlled to be 90 ℃, the adsorption time is 30min, and the stirring speed is 300r/min; and after adsorption, filtering by using a vacuum filter to realize solid-liquid separation.
(3) Desorbing, concentrating, and precipitating
Firstly, desorbing the adsorbent which is adsorbed in the step (2) by using a desorbent, wherein HCl can be used as a desorption solution, and during desorption, the desorption temperature is controlled to be 10 ℃, the desorption time is 30 hours, and the pH value of the desorption solution is 7, so that the desorption solution is finally obtained. Then, the desorption solution was concentrated to obtain a concentrated LiOH solution having a concentration of 1g/L. And finally, adding a precipitator sodium aluminate solution into one part of the concentrated solution to prepare a lithium-aluminum alkaline compound, and keeping the other part of the concentrated solution for later use.
XRD characterization was performed on the prepared lithium aluminum basic complex (lithium aluminum hydroxide) solid phase precipitate, and the result was substantially the same as in example 1.
(4) Roasting
Mixing the obtained lithium-aluminum alkaline compound in step (3) with additive, and sintering at 900 deg.C for 2 hr, wherein the additive can be other calcium-containing salts such as calcium oxide, calcium carbonate, and calcium hydroxide, wherein CaO/Al 2 O 3 The molar ratio of (1) and roasting to prepare the lithium-rich clinker.
(5) Briquetting and drying the slurry
Mixing the lithium-rich clinker obtained in the step (4) with the concentrated solution concentrated in the step (3), briquetting and drying; wherein, the radius of the obtained pellet is controlled to be 25mm, and the water content is controlled to be 16%; the temperature interval for drying the pellets is 68 ℃.
(6) Vacuum aluminothermic reduction
Crushing the mixed material mass obtained in the step (5), fully mixing with aluminum powder, and carrying out aluminothermic reduction to obtain metal lithium; when aluminothermic reduction is carried out, the molar ratio of the added metallic aluminum to the lithium in the lithium-rich clinker is 0.4, the pressure is less than 20Pa, the reduction temperature is 1000 ℃, the reduction time is 1.8h, and the generated lithium vapor is cooled and crystallized to form metallic lithium.
(7) Leaching out
And crushing the calcium aluminate slag generated after aluminothermic reduction, leaching by using a sodium carbonate solution, and performing vacuum filtration for solid-liquid separation. Wherein, before leaching, the calcium aluminate slag is ground to be below 150 μm, the leaching temperature is controlled to be 100 ℃, and Na is contained in the sodium carbonate solution 2 The concentration of O is controlled to be 100g/L, and the leaching time is 30min. Calcium carbonate obtained by leaching is used as a roasting additive and enters the step (4) for recycling; the obtained sodium aluminate solution can be used as a precipitator and recycled in the step (3).
Example 4
As shown in fig. 1, the method for preparing lithium metal by using an alkali leaching solution of an aluminum-lithium co-production resource as a raw material in the embodiment includes the following steps:
(1) Preparation of the adsorbent
The aluminum LDH adsorbing material is prepared by a self-precipitation method, and the specific preparation method comprises the following steps: firstly, preparing a sodium aluminate solution with the concentration of alumina of 170g/L and the molar ratio of sodium oxide to alumina of 1.8, adding a LiOH solution into the solution, controlling the concentration of Li ions to be 20ppm, reacting the mixed solution at 0 ℃ for 10 days, filtering in vacuum to obtain an aluminum LDH adsorption material, washing with water, and drying at 65 ℃ to obtain the adsorption material.
XRD characterization was performed on the prepared adsorbent, and the result was substantially the same as in example 1.
(2) Adsorbing and filtering
Adsorbing lithium ions in the lithium-containing sodium aluminate solution by using the adsorbent obtained in the step (1), and stirring, wherein the adsorption temperature is controlled to be 10 ℃, the adsorption time is controlled to be 48h, and the stirring speed is 260r/min; and after adsorption, filtering by using a vacuum filter to realize solid-liquid separation.
(3) Desorbing, concentrating, and precipitating
Firstly, desorbing the adsorbent which is adsorbed in the step (2) by adopting a desorbent, wherein the desorbent can adopt HNO 3 And during desorption, controlling the desorption temperature to be 90 ℃, the desorption time to be 38h, and the pH value of the desorption liquid to be 14 to finally obtain the desorption liquid. Then, the desorption solution was concentrated to obtain a concentrated LiOH solution having a concentration of 50g/L. And finally, adding a precipitator sodium aluminate solution into one part of the concentrated solution to prepare a lithium-aluminum alkaline compound, and keeping the other part of the concentrated solution for later use.
XRD characterization was performed on the prepared lithium aluminum basic complex (lithium aluminum hydroxide) solid phase precipitate, and the result was substantially the same as in example 1.
(4) Roasting
Mixing the obtained lithium-aluminum alkaline compound in step (3) with additive, and sintering at 1000 deg.C for 0.9 hr, wherein the additive can be other calcium-containing salts such as calcium oxide, calcium carbonate, and calcium hydroxide, wherein CaO/Al 2 O 3 The molar ratio of (2) and roasting to prepare the lithium-rich clinker.
(5) Briquetting and drying the slurry
Mixing the lithium-rich clinker obtained in the step (4) with the concentrated solution concentrated in the step (3), briquetting and drying; wherein, the radius of the obtained pellet is controlled to be 30mm, and the water content is controlled to be 10%; the temperature interval for drying the pellets is 50 ℃.
(6) Vacuum aluminothermic reduction
Crushing the mixed material mass obtained in the step (5), fully mixing with aluminum powder, and carrying out aluminothermic reduction to obtain metal lithium; when aluminothermic reduction is carried out, the molar ratio of the added metallic aluminum to the lithium in the lithium-rich clinker is 0.38, the pressure is less than 20Pa, the reduction temperature is 900 ℃, the reduction time is 0.5h, and the generated lithium vapor is cooled and crystallized to form the metallic lithium.
(7) Leaching out
And crushing the calcium aluminate slag generated after aluminothermic reduction, leaching by using a sodium carbonate solution, and performing vacuum filtration for solid-liquid separation. Wherein, before leaching, the calcium aluminate slag needs to be groundTo below 150 μm, and controlling leaching temperature at 85 deg.C, and adding Na in sodium carbonate solution 2 The concentration of O is controlled to be 150g/L, and the leaching time is 45min. Calcium carbonate obtained by leaching is used as a roasting additive and enters the step (4) for recycling; the obtained sodium aluminate solution can be used as a precipitator and recycled in the step (3).
Example 5
As shown in fig. 1, the method for preparing lithium metal by using an alkali leaching solution of an aluminum-lithium co-production resource as a raw material in the embodiment includes the following steps:
(1) Preparation of the adsorbent
The aluminum LDH adsorbing material is prepared by a self-precipitation method, and the specific preparation method comprises the following steps: firstly, preparing a sodium aluminate solution with the concentration of 20g/L of alumina and the molar ratio of sodium oxide to alumina being 1.6, adding a LiOH solution into the sodium aluminate solution, controlling the concentration of Li ions to be 35ppm, reacting the mixed solution at 60 ℃ for 4 days, filtering in vacuum to obtain an aluminum LDH adsorbing material, washing with water, and drying at 80 ℃ to obtain the adsorbing material.
XRD characterization was performed on the prepared adsorbent, and the result was substantially the same as in example 1.
(2) Adsorbing and filtering
Adsorbing lithium ions in the lithium-containing sodium aluminate solution by using the adsorbent obtained in the step (1), and stirring, wherein the adsorption temperature is controlled to be 30 ℃, the adsorption time is 30 hours, and the stirring speed is 240r/min; and after adsorption, filtering by using a vacuum filter to realize solid-liquid separation.
(3) Desorbing, concentrating, and precipitating
Firstly, desorbing the adsorbent which is completely adsorbed in the step (2) by using a desorbent, wherein the desorbent can be distilled water, and during desorption, the desorption temperature is controlled to be 80 ℃, the desorption time is controlled to be 48 hours, and the pH value of the desorbent is 10, so that the desorbent is finally obtained. Then, the desorption solution was concentrated to obtain a concentrated LiOH solution having a concentration of 12g/L. And finally, adding a precipitator sodium aluminate solution into one part of the concentrated solution to prepare a lithium-aluminum alkaline compound, and keeping the other part of the concentrated solution for later use.
XRD characterization was performed on the prepared lithium aluminum basic complex (lithium aluminum hydroxide) solid phase precipitate, and the result was substantially the same as in example 1.
(4) Roasting
Mixing the obtained lithium-aluminum alkaline compound in step (3) with additive, and sintering at 800 deg.C for 1.8 hr, wherein the additive can be other calcium-containing salts such as calcium oxide, calcium carbonate, and calcium hydroxide, wherein CaO/Al 2 O 3 The molar ratio of (1.3) and roasting to prepare the lithium-rich clinker.
(5) Briquetting and drying the slurry
Mixing the lithium-rich clinker obtained in the step (4) with the concentrated solution concentrated in the step (3), briquetting and drying; wherein, the radius of the pellet is controlled to be 20mm, and the water content is controlled to be 20%; the temperature interval for drying the pellets is 90 ℃.
(6) Vacuum aluminothermic reduction
Crushing the mixed material mass obtained in the step (5), fully mixing with aluminum powder, and carrying out aluminothermic reduction to obtain metal lithium; when aluminothermic reduction is carried out, the molar ratio of the added metallic aluminum to the lithium in the lithium-rich clinker is 0.36, the pressure is less than 20Pa, the reduction temperature is 850 ℃, the reduction time is 1.0h, and the generated lithium vapor is cooled and crystallized to form metallic lithium.
(7) Leaching out
And crushing the calcium aluminate slag generated after aluminothermic reduction, leaching by using a sodium carbonate solution, and performing vacuum filtration for solid-liquid separation. Wherein, before leaching, the calcium aluminate slag is ground to be below 150 μm, the leaching temperature is controlled to be 90 ℃, and Na is contained in the sodium carbonate solution 2 The concentration of O is controlled to be 95g/L, and the leaching time is 60min. Calcium carbonate obtained by leaching is used as a roasting additive and enters the step (4) for recycling; the obtained sodium aluminate solution can be used as a precipitator and recycled in the step (3).

Claims (7)

1. A method for preparing metal lithium by taking an aluminum-lithium symbiotic resource alkali leaching solution as a raw material is characterized by comprising the following steps:
(1) Preparing an adsorbent; the prepared adsorbent is an LDH adsorbing material; the preparation method of the LDH adsorbing material comprises the following steps: preparing a sodium aluminate solution with the concentration of 20-170g/L of alumina and the molar ratio of sodium oxide to alumina of 1.5-1.8, adding a LiOH solution into the sodium aluminate solution, controlling the concentration of Li ions to be 20-100ppm, reacting at 0-90 ℃ for 1d-10d, carrying out vacuum filtration, washing with water, and drying at 60-90 ℃ to obtain the adsorbing material;
(2) Adsorption and filtration: adsorbing lithium ions in the lithium-containing sodium aluminate solution by using the adsorbent obtained in the step (1), and filtering;
(3) Desorption, concentration and precipitation: firstly, desorbing the adsorbent which finishes adsorption in the step (2) by adopting a desorbent to obtain a desorption solution; then concentrating the desorption solution to obtain a concentrated lithium salt solution; finally, adding a precipitator into a part of concentrated solution to prepare a lithium-aluminum alkaline compound, and keeping the other part of concentrated solution for later use; wherein the desorbent is distilled water, HCl, HNO 3 Or H 2 SO 4 (ii) a The precipitant is sodium aluminate solution;
(4) Roasting: mixing the lithium-aluminum alkaline compound obtained in the step (3) with an additive, and roasting to prepare a lithium-rich clinker, wherein the roasting additive adopts calcium-containing salts;
(5) Slurry briquetting and drying: mixing the lithium-rich clinker obtained in the step (4) with the concentrated solution concentrated in the step (3), briquetting and drying;
(6) Vacuum aluminothermic reduction: crushing the mixed material mass obtained in the step (5), fully mixing with aluminum powder, and carrying out aluminothermic reduction to obtain metal lithium;
(7) Leaching: crushing and leaching the calcium aluminate slag generated after aluminothermic reduction, and returning the obtained calcium carbonate serving as a roasting additive to the step (4) for cyclic utilization; and (4) returning the obtained sodium aluminate solution as a precipitator to the step (3) for recycling.
2. The method for preparing the metal lithium by using the alkali leaching solution of the aluminum-lithium co-generation resource as the raw material according to claim 1, characterized in that: in the step (2), the adsorption temperature is controlled to be 10-90 ℃, the adsorption time is 30min-48h, and the stirring speed is 200-300r/min; during filtering, a vacuum filter is adopted for solid-liquid separation.
3. The method for preparing the metal lithium by using the alkali leaching solution of the aluminum-lithium co-generation resource as the raw material according to claim 1, characterized in that: in the step (3), during desorption, the desorption temperature is controlled to be 10-90 ℃, the desorption time is 30-48h, and the pH value of the desorption solution is 7-14; when concentrating, the concentration of the obtained LiOH concentrated solution is controlled to be 1-50g/L.
4. The method for preparing the metal lithium by using the alkali leaching solution of the aluminum-lithium co-generation resource as the raw material according to any one of claims 1 to 3, wherein the method comprises the following steps: in the step (4), the roasting temperature is controlled to be 750-1000 ℃, and the sintering time is 0.5-2h; in the step (5), the radius of the obtained pellets is controlled to be 10-30mm, and the water content is controlled to be 5% -20%; the temperature range for drying the pellets is 50-90 ℃.
5. The method for preparing the metal lithium by using the alkali leaching solution of the aluminum-lithium co-generation resource as the raw material according to claim 4, characterized in that: and (3) when aluminothermic reduction is carried out in the step (6), the molar ratio of the added metal aluminum to the lithium in the lithium-rich clinker is 0.3-0.4, the pressure is less than 20Pa, the reduction temperature is 750-1000 ℃, and the reduction time is 0.5-2h.
6. The method for preparing the metal lithium by using the alkali leaching solution of the aluminum-lithium co-generation resource as the raw material according to claim 5, characterized in that: in the step (7), a sodium carbonate solution is adopted for leaching, and vacuum filtration is adopted for solid-liquid separation.
7. The method for preparing the metallic lithium by using the alkali leaching solution of the aluminum-lithium co-production resource as the raw material according to claim 6, characterized by comprising the following steps: in the step (7), the calcium aluminate slag is ground to be less than 150 mu m, the leaching temperature is controlled to be 50-100 ℃, and Na is contained in the sodium carbonate solution 2 The concentration of O is controlled to be 80-150g/L, and the leaching time is 30-60min.
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